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Preface

This book is intended for chemists, chemical engineers, and others who want to see a better world through chemistry and a
transition from its present unsustainable course1 to a sustainable future.2 (A sustainable future is one that allows future gen-
erations as many options as we have today.) It is meant to serve as an introduction to the emerging field of green chemistry—
of pollution prevention. It is based on a one-semester three-credit course3 given at the senior–graduate level interface at the
University of Delaware each year from 1995 to 1998.
Books and courses in environmental chemistry usually deal with contaminants that enter air, water, and soil as a result of
human activities: how to analyze for them and what to add to the smokestack or tailpipe to eliminate them. They are also
concerned with how to get the contaminants out of the soil once they are there. Because texts such as those by Andrews et
al.,4 Baird,5 Crosby,6 Gupta,7 Macalady,8 Manahan,9 and Spiro and Stigliani10 cover this area adequately, such material need
not be repeated here.
Green chemistry11 avoids pollution by utilizing processes that are “benign by design.” (The industrial ecology12 being
studied by engineers and green chemistry are both parts of one approach to a sustainable future.) Ideally, these processes use
nontoxic chemicals13 and produce no waste, while saving energy and helping our society achieve a transition to a sustain-
able economy. It had its origins in programs such as 3M’s “Pollution Prevention Pays.” It was formalized in the United States
by the Pollution Prevention Act of 1990. Since then, the U.S. Environmental Protection Agency and the National Science
Foundation have been making small grants for research in the area. Some of the results have been summarized in symposia
organized by these agencies.14
This book cuts across traditional disciplinary lines in an effort to achieve a holistic view. The material is drawn from in-
organic chemistry, biochemistry, organic chemistry, chemical engineering, materials science, polymer chemistry, conserva-
tion, etc. While the book is concerned primarily with chemistry, it is necessary to indicate how this fits into the larger soci-
etal problems. For example, in the discussion of the chemistry of low-emissivity windows and photovoltaic cells, it is also
pointed out that enormous energy savings would result from incorporating passive solar heating and cooling in building de-
sign. Living close enough to walk or bike to work or to use public transportation instead of driving alone will save much
more energy than would better windows. (Two common criticisms of scientists is that their training is too narrow and that
they do not consider the social impacts of their work.)
This book begins with a chapter on the need for green chemistry, including the toxicity of chemicals and the need for min-
imization of waste. The next three chapters deal with the methods that are being studied to replace some especially noxious
materials. Chapters 5–8 cover various ways to improve separations and to reduce waste. Chapter 9 continues this theme and
switches to combinations of biology and chemistry. Chapter 10 discusses many optical resolutions done by enzymes or
whole cells. Chapter 11, on agrochemicals, continues the biological theme. Chapters 12 through 15 cover various aspects of
sustainability, such as where energy and materials will come from if not from petroleum, natural gas, or coal; how to pro-
mote sustainability by making things last longer; and the role of recycling in reducing demands on the natural resource base.
The last three chapters try to answer the question that arises at nearly every meeting on green chemistry: Why is it taking so
long for society to implement new knowledge of how to be green?
The topics within these chapters are not confined to specific areas. For example, cyclodextrins are discussed not only un-
der supported reagents, but also under separations by inclusion compounds or under chemistry in water. Surfactants have

iii
iv Preface

been placed under doing chemistry in water. They are also mentioned as alternatives for cleaning with organic solvents and
in the discussion on materials from renewable sources. An effort has been made to cross-reference such items. But for the
reader who has any doubt about where to find an item, a comprehensive index is included.
The industrial chemistry on which much green chemistry is based may be foreign to many in academia, but many good
references are available.15 There is much more emphasis in industrial chemistry on catalysis and the organometallic mech-
anisms that often go with them. Improved catalysts are often the key to improved productivity, using less energy and gener-
ating less waste.16 Again, many good sources of information are available.17 In addition, there are two books on the chem-
istry and biology of water, air, and soil.18
Each chapter in Introduction to Green Chemistry lists recommended reading, consisting primarily of review papers and
portions of books and encyclopedias. This allows detailed study of a subject. The introductions to current journal articles
often contain valuable references on the status of a field and trends in research. However, the traditional grain of salt
should be applied to some news items from trade journals, which may be little more than camouflaged advertisements.
The examples in the book are drawn from throughout the world. In the student exercises that accompany each chapter,
readers are often asked to obtain data on their specific location. In the United States, one need look no further than the local
newspaper for the results of the toxic substances release inventory. This data can also be found on websites of the U.S. En-
vironmental Protection Agency (http://www.epa.gov/opptintr/tri) and state environmental agencies,19 as well as on compa-
rable websites of other countries (e.g., http:// www.unweltbundesamt.de for the German environmental agency). Non-
governmental organizations also post some of this data (e.g., the Environmental Defense “Chemical Scorecard,”
www.scorecard.org, and the Committee for the National Institute for the Environment, www.cnie.org). The data available
on the Internet is growing rapidly.20 The environmental compliance records of more than 600 U.S. companies can be found
at http://es.epa.gov/oeca/sfi/index.html. A catalog of U.S. Environmental Protection Agency documents can be found at
http://www.epa.gov/ ncepihom/catalog.html. Data on the toxic properties of chemicals can be found at toxnet.nlm.nih.gov
and http:// www.chemquik.com.
Some of the exercises sample student attitudes. Others call for student projects in the lab or in the community. Some of
the questions are open-ended in the sense that society has yet to find a good answer for them, but they leave room for dis-
cussion.
Those using this volume as a textbook will find field trips helpful. These might include visits to a solar house, a farm us-
ing sustainable agriculture, a tannery, a plant manufacturing solar cells, etc. Although the course at the University of
Delaware had no laboratory, one would be useful to familiarize students with techniques of green chemistry that they might
not encounter in the regular courses. These might include the synthesis, characterization, and evaluation of a zeolite, running
a reaction in an extruder, using a catalytic membrane reactor, adding ultrasound or microwaves to a reaction, making a chem-
ical by plant cell culture, doing biocatalysis, making a compound by organic electrosynthesis, running a reaction in super-
critical carbon dioxide, and use of a heterogeneous catalyst in a hot tube. Ideally, students would run a known reaction first,
then an unknown one of their own choice (with appropriate safety precautions). Such a lab would require the collaboration
of several university departments.
There is a myth that green chemistry will cost more. This might be true if something was to be added at the smokestack
or outlet pipe. However, if the whole process is examined and rethought, being green can save money. For example, if a pro-
cess uses solvent that escapes into the air, there may be an air pollution problem. If the solvent is captured and recycled to
the process, the savings from not having to buy fresh solvent may be greater than the cost of the equipment that recycles it.
If the process is converted to a water-based one, there may be additional savings.
It is hoped that many schools will want to add green chemistry to their curricula. Sections of this book can be used in other
courses or can be used by companies for in-house training. The large number of references makes the book a guide to the lit-
erature for anyone interested in a sustainable future.

Albert S. Matlack

REFERENCES

1. J. Lubchenko, Science, 1998, 279, 491.

2. (a) R. Goodland and H. Daly. Ecol. Appl., 1996, 6, 1002. (b) A. Merkel, Science, 1998, 281: 336.
3. A.S. Matlack, Green Chem, 1999, 1(1): G17.
4. J.E. Andrews, P. Brimblecombe, T.D. Jickells, P.S. Liss, eds. Introduction to Environmental Chemistry. Blackwell Science, Cam-
bridge, MA 1995.
Preface v

5. C.L. Baird, Environmental Chemistry, W.H. Freeman, New York, 1995.

6. D.G. Crosby, Environmental Toxicology and Chemistry, Oxford University Press, New York, 1998.
7. R.S. Gupta, Environmental Engineering and Science: An Introduction, Government Institutes, Rockville, MD, 1997.
8. D.L. Macalady, Perspectives in Environmental Chemistry, Oxford University Press, Oxford, England, 1997.
9. S.E. Manahan, Environmental Chemistry, 6th ed., Lewis Publishers, Boca Raton, FL, 1994; Fundamentals of Environmental Chem-
istry, Lewis Publishers, Boca Raton, FL, 1993.
10. T.C. Spiro, W.M. Stigliani, Chemistry of the Environment, Prentice Hall, Upper Saddle River, NJ, 1996.
11. J. Clark, Chem Br, 1998, 34(10): 43.
12. (a) B. Hileman, Chem Eng News, July 20, 1998, 41; (b) J. Darmstadter, Chem Eng News, August 10, 1998, 6; (c) N.E. Gallopou-
los, Chem Eng News, August 10, 1988, 7; (d) T.E. Graedel, B.R. Allenby, Industrial Ecology, 1995; Design for Environment, 1996;
Industrial Ecology and the Automobile, 1996, all from Prentice Hall, Paramus, NJ. (e) B.R. Allenby, Industrial Ecology: Policy
Framework and Implementation, Prentice Hall, Paramus, NJ, 1998.
13. A.W. Gessner, Chem. Eng. Prog., 1998, 94(12), 59.
14. (a) Anon., Preprints ACS Div. Environ Chem, 1994, 34(2), pp. 175–431. (b) P.T. Anastas, C.A. Farris, eds. Benign by Design: Al-
ternative Synthetic Design for Pollution Prevention, ACS Symp. 577, Washington, D.C., 1994; (c) P.T. Anastas, T.C. Williamson,
eds. Green Chemistry: Designing Chemistry for the Environment, ACS Symp 626, Washington, D.C., 1996; (d) S.C. DeVito, R.L.
Garrett, eds. Designing Safer Chemicals: Green Chemistry for Pollution Prevention, ACS Symp. 640, Washington, D.C., 1996;
Chemtech, 1996, 26(11):34. (e) J.J. Breen, M.J. Dellarco, eds. Pollution Prevention in Industrial Processes: The Role of Process An-
alytical Chemistry, ACS Symp. 508, Washington, D.C., 1994. (f) P.T. Anastas, T.C. Williamson, eds. Green Chemistry: Frontiers
in Benign Chemical Syntheses and Processes, Oxford University Press, Oxford, England, 1998.
15. (a) W. Buchner, R. Schliebs, G. Winter, K.H. Buchel, Industrial Inorganic Chemisty, VCH, Weinheim, 1989; (b) K. Weissermel,
H.-J. Arpe, Industrial Organic Chemistry, 3rd ed., VCH, Weinheim, 1997. (c) P.J. Chenier, Survey of Industrial Chemistry, 2nd ed.,
VCH, Weinheim, 1992; (d) H. Wittcoff, B. Reuben, Industrial Organic Chemicals, 2nd ed., John Wiley, New York, 1996; (e) J.I.
Kroschwitz, ed. Kirk-Othmer Encyclo Chem Technol, 4th ed., John Wiley, 1991; (f) J.I. Kroschwitz, ed. Encyclo Polymer Sci and
Eng, 2nd ed., John Wiley, New York, 1985–1989; (g) W. Gerhartz, ed., Ullmann’s Encyclo Ind Chem, 5th ed., VCH, Weinheim,
1985.
16. J. Haber, Pure Appl Chem, 1994, 66: 1597
17. (a) J.N. Armor, Environmental Catalysis, A.C.S. Symp. 552, Washington, D.C., 1993; (b) G.W. Parshall, S.D. Ittel, Homogeneous
Catalysis, 2nd ed. John Wiley, New York, 1992; (c) B.C. Gates, Kirk-Othmer Encyclo Chem Technol, 4th ed., 1993, 5, 320; (d) W.R.
Moser, D.W. Slocum, eds., Homogeneous Transition Metal-Catalyzed Reactions, Adv Chem 230, American Chemical Society,
Washington, D.C., 1992; (e) J. P. Collman, L. S. Hegedus, Principles and Applications of Organotransition Chemistry, University
Science Books, Mill Valley, CA, 1980; (f) C. Elschenbroich, A. Salzer, Organometallics—A Concise Introduction, VCH, Weinheim,
1992; (g) G. Braca, Oxygenates by Homologation or CO Hydrogenation with Metal Complexes, Kluwer Academic Publishers, Dor-
drect, The Netherlands, 1994; (h) F.P. Pruchnik, Organometallic Chemistry of the Transition Elements, Plenum, NY, 1993.
18. (a) J. Tolgyessy, ed., Chemistry and Biology of Water, Air, Soil—Environmental Aspects, Elsevier, Amsterdam, 1993; (b) B. Evan-
gelou, Environmental Soil and Water Chemistry, Wiley, NY, 1998.
19. A. Kumar, R. Desai, R. Kumar, Environ. Prog., 1998, 17(2), S11. (gives a directory of World Wide Web sites)
20. (a) S.M. Bachrach, ed., The Internet: A Guide for Chemists, American Chemical Society, Washington, D.C., 1996; (b) T. Murphy,
C. Briggs-Erickson, Environmental Guide to the Internet, Government Institutes, Rockville, MD, 1998; (c) K. O’Donnell, L.
Winger, The Internet for Scientists, Harwood, Amsterdam, 1997; (d) L.E.J. Lee, P. Chin, D.D. Mosser, Biotechnol. Adv., 1998, 16:
949; (e) B.J. Thomas, The World Wide Web for Scientists and Engineers, SAE International, Warrendale, PA, 1998; (f) S. Lawrence,
C.L. Giles, Science, 1998, 280: 98; (g) R.E. Maizell, How To Find Chemical Information: A Guide for Practicing Chemists, Edu-
cators and Students, Wiley, NY, 1998.
Contents

Preface iii

1. INTRODUCTION 1

I. General Background 1
II. Toxicity of Chemicals in the Environment 2
III. Accidents with Chemicals 6
IV. Waste and Minimization 13
V. Conclusions 18
VI. Summary of Some Important Points 19
References 20
Recommended Reading 25
Exercises 25

2. DOING WITHOUT PHOSGENE 27

I. Introduction 27
II. Preparation of Isocyanates 28
III. Polycarbonates 39
IV. Summary and Conclusions 39
References 42
Recommended Reading 45
Exercises 45

3. THE CHLORINE CONTROVERSY 47

I. The Problem 47
II. Toxicity of Chlorine Compounds 50
III. Estrogen Mimics 51
IV. Bleaching Paper 52
V. Disinfecting Water 53
VI. Chlorofluorocarbons and Ozone Depletion 54
VII. Chlorinated Solvents 57
VIII. Syntheses Where the Chlorine Is Not in the Final Product 58

vii
viii Contents

IX. Summary and Conclusions 60

References 61
Recommended Reading 66
Exercises 66

4. TOXIC HEAVY METAL IONS 67

I. The Problem 67
II. End-of-the-Pipe Treatments 70
III. Biocides 72
IV. Catalysts for Reactions Other than Oxidation 74
V. Dyes and Pigments 75
VI. Electrical Uses 76
VII. Leather 77
VIII. Metal Finishing 77
IX. Oxidation 78
X. Miscellaneous 94
References 94
Recommended Reading 101
Exercises 101

5. SOLID CATALYST AND REAGENTS FOR EASE OF WORKUP 101

I. Introduction 103
II. The Use of Inorganic Supports 105
III. Ion-Exchange Resins 114
IV. Combinatorial Chemistry 118
V. Other Uses of Supported Reagents 120
VI. Cyclodextrins 126
References 128
Recommended Reading 135
Exercises 135

6. SOLID ACIDS AND BASES 137

I. Introduction 137
II. Polymeric Sulfonic Acids 138
III. Polymer-Supported Lewis Acids 139
IV. Sulfated Zirconia 140
V. Supported Metal Oxides 141
VI. Rare Earth Triflates 141
VII. Solid Bases 144
VIII. Zeolites and Related Materials 145
IX. Clays 155
X. Heteropolyacids 159
References 163
Recommended Reading 173
Exercises 173

7. CHEMICAL SEPARATIONS 175

I. The General Picture 175

II. Inclusion Compounds 178
Contents ix

III. Separation of Ions 182

IV. Membrane Separations 185
References 192
Recommended Reading 200
Exercises 200

8. WORKING WITHOUT ORGANIC SOLVENTS 201

I. Advantages and Disadvantages of Solvents 201

II. Working Without Solvents 203
III. Reactions in Extruders 207
IV. Carbon Dioxide as a Solvent 210
V. Water as a Reaction Medium 214
VI. Surfactants and Cleaning 220
VII. Coatings 223
References 228
Recommended Reading 229
Exercises 229

9. BIOCATALYSIS AND BIODIVERSITY 241

I. Biocatalysis 241
II. Biodiversity 267
References 275
Recommended Reading 288
Exercises 288

10. STEREOCHEMISTRY 291

I. The Importance of Optical Isomers 291

II. The Chiral Pool 292
III. Resolution of Racemic Mixtures 295
IV. Asymmetric Synthesis 301
References 314
Recommended Reading 318
Exercises 318

11. AGROCHEMICALS 319

I. The Nature and Use of Agrochemicals 319

II. Problems with Agrochemicals 322
III. Alternative Agriculture 326
IV. Lawns 345
V. Genetic Engineering 346
VI. Integrated Pest Management 347
References 348
Recommended Reading 358
Exercises 358
x Contents

12. MATERIALS FOR A SUSTAINABLE ECONOMY 361

I. Introduction 361
II. Commodity Chemicals from Renewable Raw Materials 361
III. Use of Natural Polymers 372
IV. Polymers from Renewable Raw Materials 374
V. Conclusions and Recommendations 379
References 379
Recommended Reading 385
Exercises 385

13. CHEMISTRY OF LONGER WEAR 387

I. Why Things Wear Out 387

II. Stabilizers for Polymers 389
III. Lubrication, Wear, and Related Subjects 395
IV. Inhibition of Corrosion 397
V. Mending 400
VI. Miscellaneous 400
VII. The Future 401
References 401
Recommended Reading 405
Exercises 405

14. CHEMISTRY OF RECYCLING 407

I. Waste 407
II. Recycling 408
III. Methods and Incentives for Source Reduction 424
IV. The Overall Picture 431
References 432
Recommended Reading 440
Exercises 440

15. ENERGY AND THE ENVIRONMENT 441

I. Energy-Related Problems 441

II. Heating, Cooling, and Lighting Buildings 449
III. Renewable Energy for Electricity and Transport 454
IV. Use of Less Common Forms of Energy for Chemical Reactions 462
References 466
Recommended Reading 478
Exercises 479

16. POPULATION AND THE ENVIRONMENT 481

I. The Problems 481

II. Chemistry of Human Reproduction 483
III. The Chemistry of Family Planning 485
IV. Summary of the Problem 491
Contents xi

References 492
Recommended Reading 495
Exercises 495

17. ENVIRONMENTAL ECONOMICS 497

I. Introduction 497
II. Nature’s Services 497
III. Environmental Accounting 499
IV. Corporations 503
V. Environmental Economics of Individuals 505
VI. Government Actions Affecting Environmental Economics 507
References 511
Recommended Reading 515
Exercises 515

18. GREENING 517

I. Introduction 517
II. Individuals 517
III. Nongovernmental Organizations 519
IV. Government 521
V. Corporations 523
References 529
Recommended Reading 534
Exercises 534

Index 535
1
Introduction
This chapter will consider what is toxic, what is waste, why
accidents occur, and how to reduce all of these.
I. GENERAL BACKGROUND
In the glorious days of the 1950s and 1960s chemists envi-
sioned chemistry as the solution to a host of society’s
needs. Indeed, they created many of the things we use to-
day and take for granted. The discovery of Ziegler–Natta
catalysis of stereospecific polymerization alone resulted in
major new polymers. The chemical industry grew by leaps
and bounds until today it employs about 1,027,000 workers
in the United States.1 Some may remember the duPont slo-
gan, “Better things for better living through chemistry.” In
the Sputnik era the scientist was a hero. At the same time,
doctors aided by new chemistry and antibiotics, felt that in-
fectious diseases had been conquered.
Unfortunately, amid the numerous success stories were
some adverse outcomes that chemists had not foreseen. It
was not realized that highly chlorinated insecticides such as
DDT [1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane]
(1.1), also known as dichlorodiphenyltrichloroethane
(made by the reaction of chloral with chlorobenzene) would
bioaccumulate in birds. This caused eggshell thinning and
nesting failures, resulting in dramatic population declines in
species such as peregrine falcon, bald eagle, osprey, and
1.1
1
brown pelican. Rachel Carson was one of the first to call at-
tention to this problem.2 Now that these insecticides have
been banned in the United States, the species are recover-
ing. Some are still made and used in other countries, but may
return to the United States by long range aerial transport
(e.g., from Mexico). (Compounds applied to plants, build-
ing surfaces, and such, may evaporate and enter the atmo-
sphere where they may remain until returned to the ground
at distant points by rain or by cooling of the air.3) DDT is
still made in Mexico, China, India, and Russia. A global
treaty to ban these persistent pollutants is being sought.4
It was also not appreciated that these compounds and
other persistent highly chlorinated compounds, such as
polychlorinated biphenyls (PCBs), can act as estrogen
mimics. Some surfactants such as those made from
alkylphenols and ethylene oxide are also thought to do this,
although perhaps to a lesser extent. The effects are now
showing up in populations of native animals, raising ques-
tions about possible effects in humans.5 A program is being
set up to screen 86,000 commercial pesticides and chemi-
cals for this property.6
Thalidomine (1.2) was used to treat nausea in pregnant
women from the late 1950s to 1962. It was withdrawn from
the market after 8000 children in 46 countries were born
with birth defects.7
1.2
2 Chapter 1
The compound has other uses as a drug as long as care is
taken not to give it to pregnant women. In Brazil it is used
to treat leprosy. Unfortunately, some doctors there have not
taken the warning seriously enough and several dozen de-
formed births have occurred.8 The U. S. Food and Drug Ad-
ministration (FDA) has approved its use for treating painful
inflammation of leprosy.9 It also inhibits human immunod-
eficiency virus (HIV) and can prevent the weight loss that
often accompanies the acquired immunodeficiency syn-
drome (AIDS). Celgene is using it as a lead compound for
an anti-inflammatory drug and is looking for analogues with
reduced side effects.10 The analogue below (1.3) is 400–500
times as active as thalidomide.
Chlorofluorocarbons were developed as safer alterna-
tives to sulfur dioxide and ammonia as refrigerants. Their
role in the destruction of the ozone layer was not antici-
pated. Tetraethyllead was used as an antiknock agent in
gasoline until it was learned that it was causing lead poi-
soning and lowering the IQ in children. We still have not
decided what to do with the waste from nuclear power
plants that will remain radioactive for longer than the
United States has been in existence. Critics still question
the advisability of using the Yucca Mountain, Nevada, site.
They say that the finding of 36Cl from atomic bomb tests in
the 1940s at the depth of the repository indicates that sur-
face water can get into this site.11
Doctors did not anticipate the development of drug-re-
sistant malaria and tuberculosis. The emergence of Legion-
naire’s disease, Lyme disease, AIDS, Hantavirus, and
Ebola virus was not anticipated. Most drug companies are
still unwilling to tackle tropical diseases because they fear
that the poor people afflicted with the diseases will not be
able to pay for the drugs.12
Today, there is often a public suspicion of scientists.
Some picture the mad chemist with his stinks and smells.
There is a notion of some people “that science is boring,
conservative, close-minded, devoid of mystery, and a neg-
ative force in society.”13 Chemophobia has increased. Many
1.3
people think that chemicals are bad and “all natural” is bet-
ter, even though a lot of them do not know what a chemical
is. There is a feeling that scientists should be more respon-
sible for the influence of their work on society. Liability
suits have proliferated in the United States. This has caused
at least three companies to declare bankruptcy: Johns
Manville for asbestos in 1982, A. H. Robins for its “Dalkon
Shield” contraceptive device in 1985, and Dow Corning for
silicone breast implants in 1995.14 Doctors used to be the re-
spected pillars of their communities. Today they are the sub-
jects of malpractice suits, some of which only serve to in-
crease the cost of health care. Medical implant research is
threatened by the unwillingness of companies such as
duPont and Dow Corning to sell plastics for the devices to
the implant companies.15 The chemical companies fear lia-
bility suits. Not long ago drug companies became so con-
cerned about law suits on childhood vaccines that many
were no longer willing to make them. Now that the U. S.
Congress has passed legislation limiting the liability, vac-
cine research is again moving forward. The law suits had not
stimulated research into vaccines with fewer side effects,
but instead had caused companies to leave the market.
II. TOXICITY OF CHEMICALS IN THE
ENVIRONMENT
The public’s perception of toxicity and risk often differs
from that found by scientific testing.16 The idea that “natu-
ral”17 is better than “chemical” is overly simplistic. Many
chemicals found in nature are extremely potent biologi-
cally. Mycotoxins are among these.18 Aflatoxins (1.4) were
discovered when turkeys fed moldy ground nut (peanut)
meal became ill and died. They are among the most potent
carcinogens known.
Vikings went berserk after eating derivatives of lysergic
acid (1.5) made by the ergot fungus growing on rye.
Some Amanita mushrooms are notorious for the poisons
that they contain. A Japanese fish delicacy of globe fish or
1.4
Introduction
1.5
other fishes may contain potent poisons (such as
tetrodotoxin; 1.6) if improperly prepared.19 Tainted fish
cause death in 6–24 h in 60% of those who consume it.
They die from paralysis of the lungs. Oysters may also con-
tain poisons acquired from their diet. The extract of the
roots of the sassafras tree (Sassafras albidum) (1.7) used to
flavor the soft drink, “root beer,” contains the carcinogen
safrole, which must be removed before use.
The natural insecticide Sabadilla, which is popular with
organic farmers, contains 30 alkaloids present at a level of
3–6% in the seeds of Schoenocaulon officinale.235 It can af-
fect the cardiovascular system, respiration, nerve fibers,
and skeletal muscles of humans. Gastrointestinal symp-
toms and hypotension may also result from its ingestion.
The U. S. Congress added the Delaney clause to the
Food, Drug, and Cosmetic Act in 1958.20 The clause reads
“No additive shall be deemed to be safe if it is found to in-
duce cancer when ingested by man or animal, or if it is
found, after tests which are appropriate for the evaluation of
the safety of food additives, to induce cancer in man or an-
imal.” It does not cover natural carcinogens in foods or en-
vironmental carcinogens, such as chlorinated dioxins and
polychlorinated biphenyls. The Delaney clause was used to
ban saccharin in 1973, but the U. S. Congress overrode this
1.6
3
1.7
prohibition with a special law that permits the use of this ar-
tificial sweetener. It is now thought to be a carcinogen for
rodents, but not for humans. Almost every tube of tooth-
paste in the United States contains it. An advisory panel of
the U. S. National Toxicology Program recommends that it
be classed as an “anticipated” human carcinogen.21
Some Americans feel that food additives are an impor-
tant source of cancer, and that the Delaney clause should be
retained. Bruce Ames, the father of the Ames test for mu-
tagens, disagrees.22 He feels that the very high doses of
chemicals that are fed to rats to speed up the tumor-form-
ing process may bear little relation to reality. He feels that
this protocol alone may cause some of the tumors. Analyt-
ical chemists are able to detect much smaller amounts of
contaminants in foods today than in 1958. A new technique
of accelerator mass spectrometry with 14C-labeled com-
pounds offers promise in testing at much closer to the real
levels consumed.23 Is there a level below which a carcino-
gen affords no risk? A single mutation can lead to cancer.
However, Abelson has pointed out that mutations occur all
the time and are eliminated by the normal DNA repair
mechanisms.24 He feels that these cover both natural and
synthetic compounds. Thus, the usual type of dose–re-
sponse curve should apply here as well. Ames, Abelson,
and others felt that the zero risk called for by the Delaney
clause had outlived its usefulness and should be replaced
by a negligible risk standard.25 The Delaney clause was re-
pealed on August 3, 1996.26
Ames feels that, instead of worrying so much about the
last traces of contaminants in foods, we should focus our at-
tention on the real killers.
Annual Preventable Deaths in the United States27
Active smoking 430.700
Alcoholic beverages 100,000
Passive smoking 53,000
Auto accidents 43,300
AIDS 37,500
Homicides 24,926
Fires 3,200
Cocaine 4,202
Heroin and morphine 4,175
Radon, to nonsmokers 2,500
4 Chapter 1
The World Health Organization (WHO) estimates the
number of smoking deaths worldwide to be about 3
million/y.28 Cigarette use is increasing among American
college students, despite these statistics.29 Indoor radon
contributes to about 12% of the lung cancer deaths in the
United States each year.30 Infectious diseases cause 37% of
all deaths worldwide.31 Many of these could be prevented
by improved sanitation. There are 3 million pesticide poi-
sonings, including 220,000 fatalities and 750,000 chronic
illnesses, in the world each year. Smoke from cooking with
wood fires kills 4 million children in the world each year.
It is estimated that perhaps 80% of cancers are environ-
mental in origin and related to lifestyle. (There are genetic
factors, now being studied by the techniques of molecular
biology, that predispose some groups to heightened risk,
e.g., breast cancer in women.32) In addition to cancers
caused by tobacco and ethanol, there are those caused by a
high fat diet,33 too much sun, smoked foods, foods pre-
served with a lot of salt, and viruses (for cancers of the liver
and cervix). Consumption of the blue–green alga, Micro-
cystis, has increased liver cancer in China. Perhaps the
biggest killer is sodium chloride, a compound necessary for
life, that plays a role in the regulation of body fluids and
blood pressure.34 It raises the blood pressure of many of the
50 million Americans with hypertension, increasing the
risk of osteoporosis, heart attack, and stroke.35 The U. S.
National Academy of Sciences suggests limiting consump-
tion of sodium chloride to 6 g/day (2.4 g of sodium). This
means cutting back on processed foods (source of 80% of
the total), such as soups, frozen dinners, salted snacks,
ham, soy sauce (18% salt), ready-to-eat breakfast cereals,
and others. However, this may not be the whole story. If
there is an adequate intake of calcium, magnesium, and
potassium, together with fruits and vegetables in a low-fat
diet, the sodium may not need to be reduced, as shown in a
1997 study.36 In the United States, snacks and soft drinks
have tended to supplant nutrient-rich foods, such as fruits,
vegetables, and milk. Not eating fruits and vegetables
poses a greater cancer risk than the traces of pesticides in
foods.37 Fruits and vegetables often contain natural antiox-
idants,38 such as the resveratrol (1.8) found in grapes. It in-
hibits tumor initiation, promotion and progression.39
1.8
Antioxidants have also reduced athersclerotic heart dis-
ease.40 Thus, foods contain many protective substances, as
well as some antinutrients, such as enzyme inhibitors and
natural toxins.41
A U. S. National Research Council report concludes that
natural and synthetic carcinogens are present in human
foods at such low levels that they pose little threat.42 It
points out that consuming too many calories as fat, protein,
carbohydrates, or ethanol is far more likely to cause cancer
than consuming the synthetic or natural chemicals in the
diet. However, it also mentions several natural substances
linked to increased cancer risk: heterocyclic amines formed
in the overcooking of meat; nitrosoamines, aflatoxins, and
other mycotoxins.43 Typical of the heterocyclic amine mu-
tagens are compounds 1.9 and 1.10, the first from fried beef
and the second from broiled fish:44
Two reviews cover the incidence of cancer and its pre-
vention by diet and other means.45 Cancer treatments have
had little effect on the death rates, so that prevention is the
key.46
Being sedentary is a risk factor for diseases such as heart
attack and late-onset diabetes. One-third of adult Ameri-
cans are obese, perhaps as much the result of cheap gaso-
line as the plentiful supply of food.47 Obesity-related com-
plications result in 300,000 premature deaths in the United
States each year. This is less of a problem in most other
countries. For example, the incidence of obesity in the
United Kingdom is 15–16.5%.
Prevention of disease is under-used.48 Needle ex-
change programs could prevent 17,000 AIDS infections in
the United States each year. Vaccines are not used
1.9
1.10
Introduction
enough. For example, only 61% of the people in Mas-
sachusetts are fully vaccinated. Only 15–30% of the el-
derly, immunocompromised persons, and those with pul-
monary or cardiac conditions have been vaccinated
against pneumonia. A 1998 study, in New Jersey and
Quebec, of patients older than 65 who had been pre-
scribed cholesterol-lowering drugs found that on the aver-
age the prescription went unfilled 40% of the year. Good
drug compliance lowered cholesterol level 39%, whereas
the poor compliance lowered it only 11%.49
Many persons take unnecessary risks by using alterna-
tive, rather than conventional, medicine. Although some of
it works (e.g., a Chinese herbal medicine for irritable bowel
syndrome), much of it is ineffective.50 The use of herbal
extracts and dietary supplements may help some people,
but many such materials are ineffective and may be dan-
gerous.51 One lot of “Plantago” contained digitalis that sent
two people to hospital emergency rooms with heart block-
age. Cases of central nervous system depression and heavy
metal poisoning have also been reported. One child died
while being treated by herbal extracts in a case where con-
ventional medicine might have saved her life. Of 260 Asian
patent medicines bought in California stores, 83 contained
undeclared pharmaceuticals or heavy metals, and 23 con-
tained more than one adulterant. Tests of ten brands of St.
John’s Wort, a popular herbal antidepressant, found that
two had 20% of the potency listed on the label, six had
50–90%, and two had 30–40% more than that listed.52 The
problem is that the U. S. Dietary Supplement Health and
Education Act of 1994, said to have been passed by strong
industry lobbying, does not allow the Food and Drug Ad-
ministration to regulate these materials. Herbal extracts are
also used in many other countries.53 The most research on
them has been done in Germany, where the Bundesinstitut
fur Arzneimittel und Medizinproduckte regulates them
more effectively than is done in the United States. Many of
the drugs used by conventional medicine originated in folk
1.12
5
1.11
medicine. These were all tested carefully for safety and ef-
ficacy, and provided in consistent standardized amounts,
before acceptance by conventional medicine. The National
Institues of Health Office of Dietary Supplements in the
United States has an international database at http://di-
etary/supplements.info.nih.gov. See also www.amfounda-
tion.org/herbmed.htm.
An additional note of caution must be added to this
discussion. Tryptophan, (1.11) an essential amino acid for
humans, was sold in health food stores as a sleeping pill.54
It was taken off the market in 1989 after a lot made by a
new microorganism at Showa Denko caused an outbreak of
a rare blood disease that killed 39 people.55 Although the
material was 99% pure, it contained over 60 trace
contaminants.
The deadly contaminants compounds 1.12 and 1.13
were present at about 0.01%. The moral is to test products
from new processes on animals first. Some samples of
over-the-counter 5-hydroxy-L-tryptophan contained impu-
rities that caused eosinophila–myalgia syndrome.56
Another sad saga resulted from the sale, by itinerant
salesmen in Spain, of aniline-denatured rapeseed oil for
cooking.57 The toxic oil syndrome affected 20,000 people
killing 839. The toxic compound is thought to have been
compound 1.14.
Research on the long-term effects of low-level pollution
continues. Air pollution by ozone, sulfur dioxide, and par-
ticulates in Britain kills 24,000 people annually.58 It is es-
timated that exposure to diesel exhaust over a 70-year life-
time will cause 450 cases of cancer per million people in
California.59 Epidemiologists continue to investigate clus-
ters of diseases such as the two to four times higher inci-
dence of neural tube and certain heart defects in children
born within 1⁄4 mile of Superfund sites in California,60 the
lower birth weight and prematurity of infants born to
1.13
6 Chapter 1
1.14
women living next to the Lipari landfill in New Jersey,61
the brain cancers in researchers at the Amoco laboratory in
Napierville, Illinois and at the University of Maine,62 and a
cancer cluster near a Superfund site at Toms River, New
Jersey. A U. S. General Accounting Office report suggests
that the list of the Superfund sites may have to be doubled
because of ground and drinking water contamination.63
Some persons may have multiple chemical sensitivities to
low levels of pollutants.64
Children are more sensitive to chemicals than adults.65
Childhood cancer and asthma are both rising. Pregnant
women who smoke tend to have more low birth weight ba-
bies and those who drink alcoholic beverages risk fetal al-
cohol syndrome. Environmental standards are often set us-
ing a statistical approach.66 The U. S. Environmental
Protection Agency sets pesticide limits at 1% of the level
found to have no effects in animals. A 1996 law to protect
children may lower this level another tenfold. Some pesti-
cide makers have gone to tests of pesticides on adult hu-
mans in the United Kingdom, presumably in an effort to
obtain higher limits.67 Some people consider this unethical.
Chemical safety is an international challenge.68 Complete
health effects data are available for only about 7% of the
chemicals produced in more than 1 million lb annually.69
The U. S. Environmental Protection Agency and the Amer-
ican Chemistry Council (formerly the Chemical Manufac-
turers Association) have reached an agreement to test 3000
chemicals in an effort to speed up the work being done by
the OECD in Europe. At first the Synthetic Organic Chem-
ical Manufacturers Association did not agree with the way
that this testing will be done,70 but agreed to it later. Ani-
mal rights activists have objected to the tests because ani-
mals will be used in at least some of the testing.71
Green chemistry chooses less toxic materials over more
toxic ones and tries to minimize the use of flammable, explo-
sive, or highly reactive materials.72 It is not always easy to fig-
ure out which is least toxic. Toxicities can vary with the
species as well as with the age and sex of the animal. The man-
ner of application may also vary. This is illustrated in the fol-
lowing by some LD50 (50% of the animals die) data on chem-
icals that are not very toxic and some that are very toxic.73
Ethanol 10.6 g/kg for young rats; 7.6g/kg for old
rats
Malathion 1.0 g/kg for female rats; 1.375 g/kg for
male rats
Glyphosate 4.873 g/kg for rats; 1.568 g/kg for mice
HCN Average fatal dose for a human;
50–60 mg
Aflatoxin 18.2 mg/50 g body weight day-old
duckling
Acetone 10.7 ml/kg orally for rats
This test probably would not pick up long-term effects
caused by bioaccumulation. Populations of animals can
also be decimated by chemical effects that do not kill the
animals (e.g., the egg shell thinning of birds at the top of the
food chain, feminization of males, and behavioral changes,
such as not feeding or protecting the young, or losing the
ability to avoid predators).
Many chemists alive today have worked with com-
pounds later found to be carcinogens, neurotoxins, and so
on. All chemicals need to be treated with due respect.74
III. ACCIDENTS WITH CHEMICALS
Chemists take pride in their ability to tame dangerous
chemicals to make the things society needs. In fact, some
companies seek business by advertising their ability to do
custom syntheses with such chemicals. Aerojet Fine Chem-
icals offers syntheses with azides and vigorous oxida-
tions.75 Carbolabs offers custom syntheses with phosgene,
fluorinating agents, and nitration. Custom syntheses with
phosgene are also offered by PPG Industries, Hatco,
Rhone-Poulenc, and SPNE (see Chap 2). A hazardous
reagent may be attractive for fine chemical syntheses if it
gives a cleaner product with less waste or saves two or
three steps. It may also be used because it is the traditional
way of doing the job.
Chemistry is a relatively safe occupation. (Underground
coal mining is one of the most dangerous in the United
States. A total of 47 coal miners lost their lives in 1995
from surface and underground mining.76) In the United
States in 1996, the nonfatal injury and illness rate for chem-
ical manufacturing was 4.8:100 full-time workers, com-
pared with 10.6 for all of manufacturing. There were 34
deaths in the chemical industry, about 5% of those for all
manufacturing.77 The injury rate of the chemical industry
in the United Kingdom fell to an all time low in 1997, 0.37
accidents per 100,000 h. This was in the middle of those for
manufacturing industries, worse than the textile industry,
but better than the food, beverage, and tobacco industries.78
However, despite countless safety meetings and inspec-
tions and safety prizes, accidents still happen.79 In chem-
Introduction
istry, just as in airline safety, some of the accidents can be
quite dramatic. There were 23,000 accidents with toxic
chemicals in the United States in 1993–1995 (i.e., 7670/yr
compared with 6900/yr in 1988–1992. The accidents in
1993–1995 included 60 deaths and the evacuation of
41,000 people. Statistics for the United States compiled by
the Chemical Safety and Hazard Investigation Board reveal
an average of 1380 chemical accidents resulting in death,
injury, or evacuation each year for the 10 years before
1999.80 Each year, these accidents caused an average of
226 deaths and 2000 injuries. About 60,000 chemical acci-
dents are reported annually in the United States. The Amer-
ican Chemistry Council in the United States reported 793
fires, explosions, and chemical releases in 1995.81
There is usually an investigation to determine the cause
of an accident. Knowing the cause should help eliminate
similar accidents in the future. Then engineering steps may
be taken to produce a fail-safe system. These may involve
additional alarms, interlocks (such as turning off the mi-
crowaves before the oven door can be opened), automatic
shut-offs if any leaks occur, and secondary vessels that
would contain a spill. A special sump contained a leak of
nerve gas when an O-ring failed at an incinerator at Tooele,
Utah.82 Underground storage tanks (made of noncorroding
materials) may be fitted with a catchment basin around the
fill pipe, automatic shut-off devices to prevent overfilling,
and a double wall complete with an interstitial monitor.83
Clearly, such methods can work, but they have not reduced
the overall incidence of accidents, as shown in the forego-
ing data. The best solution will be to satisfy society’s needs
with a minimum of hazardous chemicals.84 A few of the
many accidents will be discussed in the following to show
how and why they occurred, together with some green ap-
proaches that could eliminate them.
The chemical industry received a wake-up call for im-
proved safety when 40 tons of methyl isocyanate escaped
from a pesticide plant into a densely populated area of
Bhopal, India on Dec. 3, 1984. This resulted in 3500 deaths
and 150,000 injuries.85 According to one reviewer86 the
accident
. . . was the ultimate outcome of faulty technolog-
ical design, years of poor management of an unprof-
itable and highly dangerous facility, years of ignor-
ing an outrageously bad safety record on the part of
both the parent company and the Indian government,
inadequate education and training of the work force,
uncontrolled growth of an industrial population cen-
ter, a nonexistent emergency response system and the
community’s ignorance about the dangers in its
midst.
7
At the time of the accident, a refrigeration system, a tem-
perature indicator, and a flare tower were not functioning.87
Curiously, the Maharashtra Development Council (in the
state next to the one in which Bhopal is located) advertised
in 1998
. . . The strengthening of the green movement and
the growing protests against environmental pollution
in many Western countries provide an opportunity
for India to emerge as a major player in the global
dye market. Given the global tendency to take full
advantage of lower labor costs and less stringent
effluent legislation, India has a competitive
advantage.88
There have been 17 chemical releases that have ex-
ceeded Bhopal in volume and toxicity. Fortunately, their
locations and weather conditions prevented disasters such
as Bhopal. In 1994, failure of a storage tank at Occidental
Chemical allowed as much as 500 lb of chlorine to escape
through a hole the size of a filing cabinet.89 Fortunately, air
currents did not carry the cloud of chlorine over Delaware
City, about a mile away, or New Castle, Delaware, a few
miles to the north. (Chlorine was used as a war gas in
World War I.)
The explosion of the nuclear reactor at Chernobyl
(spelling changed recently to Chornobyl) in the Ukraine on
April 26, 1986 sent radioactive material as far away as
Sweden.90 The current death toll is 45. There has been a
huge increase in childhood thyroid cancer, with cases as far
as 500 km away.91 (U. S. bomb tests have also increased
the incidence of thyroid cancers in the western United
States.92) There is a 30-km exclusion zone around the plant
where no one is allowed to live. This was created by the
evacuation of 135,000 people.93 The accident is said to
have happened “because of combination of the physical
characteristics of the reactor, the design of the control rods,
human error and management shortcomings in the design,
and implementation of the safety experiment.”
The world’s worst radioactive contamination (twice that
of Chernobyl) is at Mayak in Russia. This has resulted from
explosion of a radioactive waste storage unit on September
29, 1957 and deliberate dumping of liquid waste into the
Techa River in 1949–1956.94
Although no nuclear plants in the United States have ex-
ploded, there have been some scary incidents. The near
melt-down at Three Mile Island, near Harrisburg, Pennsyl-
vania, involved a faulty valve. At the Salem, New Jersey,
nuclear plants there have been “repetitive equipment prob-
lems and personnel errors,” the latter including manually
overriding safety alarms.95 The Nuclear Regulatory Com-
mission shut down all three units at the site in 1995 for “re-
8 Chapter 1
peated failures in their preventive maintenance programs”
according to an ex-employee.96 Fines of more than 700,000
dollars have been imposed on the utility.97 The corporate
culture was said to be “production, production, produc-
tion.” A company official said, “We had a lackadaisical,
casual approach.”98 They were restarted after 2 years, pre-
sumably after the problems had been corrected. Since then,
there have been outages due a leak when an operator ex-
ceeded the design pressure for a coolant system and prob-
lems with a water intake system.99 In the last two decades
these power plants have operated only 52% of the time,
putting them among the 10 worst of the 110 nuclear plants
in the United States. The U. S. General Accounting Office
has questioned the effectiveness of the Nuclear Regulatory
Commission in regulating such plants.100 This is the second
largest commercial generating station in the United States.
At the Peach Bottom nuclear plant in southeastern Penn-
sylvania, an operator was found fast asleep. Federal labo-
ratories in the United States have also had problems: ex-
plosion of a solution of hydroxylamine nitrate in dilute
nitric acid at the Hanford plant in Richland, Washington
(nearly identical with earlier ones at other federal facili-
ties)101; a series of safety problems, including an explosion,
at Los Alamos, New Mexico102; and a series of seven inci-
dents, including equipment problems, leading up to the clo-
sure of the High Flux Isotope Reactor Facility at Oak
Ridge, Tennessee.103 The Oak Ridge problems included,
“Communication among all parties is inadequate and inef-
fective”; “inattention to detail”; a “significant lack of trust
and respect”; “high levels of frustration”; and too much pa-
perwork. New nuclear plants104 are no longer being built in
the United States, but large numbers are being planned for
East Asia.105 France generates 75% of its electricity from
nuclear energy. There has been an increase in the incidence
of leukemia within a 35-km radius of a nuclear waste-re-
processing plant at La Hague on the Normandy coast.106
Electricity need not be generated by nuclear power.
Generating it from fossil fuels contributes to global warm-
ing. Producing it from renewable sources, such as wind,
wave power, hydropower, geothermal, and solar energy
does not (see Chap. 15). Sweden has voted to phase out nu-
clear energy. The German government has agreed to phase
out the country’s 19 nuclear reactors.107 It has been esti-
mated that offshore wind power sources could produce
electricity 40% more cheaply than the nuclear power sta-
tions planned for Japan.108 Energy conservation can help a
great deal in reducing the amount of energy needed.
The flammable gases used by the petrochemical indus-
try have been involved in many accidents.109 A fire and
explosion following a leak of ethylene and isobutane from
a pipeline at a Phillips plant in Pasadena, Texas, in 1989,
killed 23 people and injured 130.110 The U. S. Occupa-
tional Safety and Health Administration (OSHA) fined
the company 4 million dollars. Accidents of this type can
happen anywhere in the world where the petrochemical
industry is located. There have been explosions in an
ethylene plant at Beijing, China,111 at a Shell air separa-
tions plant in Malaysia,112 a Shell ethylene and propylene
plant in Deer Park, Texas,113 a Shell propylene plant in
Norco, Louisiana,114 at a BASF plant in Ludwigshafen,
Germany, that used pentane to blow polystyrene,115 and at
a Texaco refinery at Milford Haven, England.116 The
problems at the BASF plant might have been avoided by
blowing the polystyrene with nitrogen or carbon dioxide,
instead of pentane. Two weeks before this incident at the
BASF plant, four people were injured by a fire from a
leak of benzene.117 BASF had two other accidents in Oc-
tober 1995, a polypropylene fire in Wilton, England, and
spraying of a heat transfer fluid over the plant and adja-
cent town in Ludwigshafen, Germany.118 There was an
explosion in the hydrogenation area of the company’s 1,4-
butanediol plant in Geismar, Louisiana, on April 15,
1997.119 It resulted from internal corrosion of a hydrogen
line. This corrosion might have been detected by periodic
nondestructive testing with ultrasound. The explosion and
fires at the Texaco refinery have been attributed to mak-
ing modifications in the plant, but not training people on
how to use them, having too many alarms (2040 in the
plant), insufficient inspection of the corrosion of the
equipment, not learning from past experience, and re-
duced operator staffing.120 Investigation of an explosion
and fire at Shell Chemical’s Belpre, Ohio, thermoplastic
elastomer plant revealed that
[A]t the time of the accident, roughly seven times
the normal amount of butadiene had inadvertently
been added to the reactor. Alarms indicated that the
reactor had been overcharged, but interlocks were
manually overridden to initiate the transfer of raw
materials into the reactor vessel, contrary to estab-
lished procedures.121
The federal government fined the company 3 million
dollars for the various citations in relation to the acci-
dent.122 Hoechst is another company that has had repeated
problems: “a serious pollution problem” at Griesheim, Ger-
many in 1993, as well as “seven major incidents, mostly in
Europe, between January 1995 and June 1996,” including
leaks of acrylic acid and a fire and explosion in an acetic
acid plant at Clear Lake, Texas; a fire in a 2-ethylhexanol
plant in Oberhausen, Germany; and problems with the
methanol plant in Edmonton, Alberta, Canada.123
The difference between a minor incident and a major ac-
cident with fatalities may depend on the amount of wind at
the time and whether or not a spark or a welding torch,
Introduction
which can ignite the mixture, is nearby. A switch from a
base of petroleum and natural gas to renewable resources
would eliminate many of these types of accidents. The use
of more paper and fewer plastics will help (e.g., paper bags
at supermarkets). Plastics made by biocatalysis [e.g.,
poly(lactic acid) and poly(3-hydroxybutyrate)] can be used
instead of polypropylene. Plastics made from proteins from
corn, milk, or soybeans may be able to replace many of
those derived from petrochemicals. Acetic acid can be pro-
duced by fermentation, rather than by the reaction of
methanol with carbon monoxide (a toxic gas).124 It may be
a nuisance to have to mop up a leak or spill in a fermenta-
tion plant, but it is unlikely that there will be any fire or ex-
plosion (see Chaps. 9 and 12).
Investigation of the causes of accidents should help pre-
vent recurrence of the same types, but this does not seem to
work in some cases. An explosion killed 4 employees and
injured 18 others at a Terra Industries, Port Neal, Iowa, fer-
tilizer plant.125 The Iowa fire marshall blamed an over-
heated pump, which recirculated ammonium nitrate solu-
tion, that was left running during a shutdown of the unit. It
caused water to evaporate, allowing the ammonium nitrate
to crystallize.126 The Environmental Protection Agency
(EPA) investigation concluded that the explosion resulted
from a lack of written, safe operation procedures. “In the
days and weeks just prior to the explosion equipment fail-
ures and maintenance problems were chronic.”127 Ammo-
nium nitrate has been involved in other major catastro-
phes.128 An explosion at Oppau, Germany, in September
1921 killed 1000 people. The shock was felt 145 miles
away. A “terrific explosion” of two freighters loading am-
monium nitrate containing 1% mineral oil killed 512 peo-
ple, including many in chemical plants adjacent to the
dock.129 Ammonium nitrate is used primarily as a fertilizer.
It can be replaced by crop rotations involving nitrogen-fix-
ing legumes, spreading animal manure on fields, and fewer
lawns (see Chap. 11).
An explosion at a Sierra Chemical explosives plant in
Nevada on January 7, 1998, killed four workers and in-
juried three others. The explosion occurred when an oper-
ator turned on a mixing pot motor causing detonation of ex-
plosives that had solidified on standing overnight.
Investigation by the newly activated Chemical Safety and
Hazard Investigation Board130 found that the training of
workers had been conducted “primarily in an ineffective,
informal manner that overrelied on the the use of on-the-
job training. . . . Management believed that, short of using
a blasting cap, it was almost impossible to detonate the ex-
plosive materials they used or produced.”131
These examples show that even though companies have
a great deal of experience in handling hazardous materials,
accidents can still occur. This includes toxic gases as well.
9
A leak in the hydrogen cyanide unit at a Rohm & Haas,
Deer Park, Texas plant, sent 32 workers to the hospital.132
Presumably, the hydrogen cyanide was being used to react
with acetone in the synthesis of methyl methacrylate. An
alternative route that does not use hydrogen cyanide is
available.133 Isobutylene is oxidized catalytically to
methacrolein, then to methacrylic acid, which is esterified
with methanol to give methyl methacrylate. The
methacrolein can also be made by the hydroformylation of
propyne, although this does involve the use of toxic carbon
monoxide and flammable hydrogen.134 These processes
also eliminate the ammonium bisulfate waste from the pro-
cess using hydrogen cyanide. A leak of hydrogen fluoride
at a Marathon Petroleum plant in Texas City, Texas, sent
140 people to the hospital for observation and treatment of
inflamed eyes and lungs and caused the evacuation of 3000
more.135 Replacement of the hydrogen fluoride with a non-
volatile solid acid would eliminate such problems (see
Chap. 6). Many companies in the United Kingdom do not
store hazardous materials correctly, which has resulted in
some fires and explosions.136
Stern government warnings are not enough to prevent
such releases. ICI spilled 704 lb of ethylene dichloride, in
July 1996, and 331,000 lb of chloroform, in April 1996, at
its Runcorn plant near Liverpool, England. Other leaks at
the plant involved mercury, trichloroethylene, and hex-
achlorobenzene.137 The company promised the British En-
vironment Agency that it would prevent spills in the future.
Then, on June 4, 1997, a leak of titanium tetrachloride
caused the closure of a nearby road for 2 h, and on June 5,
1997, an oil spill occurred at another site. The Environment
Agency shut down the titanium dioxide plant saying, “It is
outrageous that, within weeks of ICI being called to a meet-
ing with the Agency, where it promised to clean up its act,
its plants have been involved in two further leaks.”138
Abnormal events (i.e., the unforseen) can lead to acci-
dents. The Napp Industries Lodi, New Jersey plant was de-
stroyed by an explosion and fire on April 21, 1995, while
doing toll manufacturing. Five workers were killed, dozens
injured, and 400 nearby residents evacuated.139 A line
feeding benzaldehyde into a mixture of aluminum powder
and sodium hydrosulfite plugged. In trying to clear the
blockage workers inadvertently introduced some water.
They went home at 7:30 PM. No more was done until 6:00
AM when the morning shift arrived. Although they blan-
keted the reaction with nitrogen, continuing build-up of
heat led to the explosion at 8:00 AM. The U. S. Occupa-
tional Safety and Health Administration fined the company
127,000 dollars for 18 alleged safety and health violations
that involved “multiple mistakes and mismanagement.”140
An abnormal event in a biocatalysis plant would not cause
such problems (see Chap. 9).
10
Human error is a factor in many accidents. A 5:00 AM,
fire at a poly(vinyl chloride) pipe plant in Samson, Al-
abama, resulted in evacuation of 2500 residents within a 2-
mile radius.141 It was caused by a 40-gal mixing vat over-
heating when the heater was left on overnight by mistake.
This accident might have been avoided by putting the
heater on a timer. A better solution would be to blow the
polymer with an inert gas, such as nitrogen or carbon
dioxide.
Add to these accidents the oil spills from ships, such as
the Exxon Valdez in 1989, that lost 11 million gal of heavy
crude oil into Prince William Sound in Alaska.142 Major
spills have also occurred off of Ireland, France, Japan,
Scotland, and Spain. In February 1996, a spill of 65,000
tons occurred off of Wales.143 This, plus plant accidents at
Hoechst in the same month and the problem of disposing of
an obsolete oil platform, have resulted in a proposed set of
Integrated Pollution Prevention Control rules in Europe.
Opinions differ on how long it takes these marine ecosys-
tems to recover. Duck, murre, and sea otter populations in
Alaska may take years to recover.144 Measures suggested
by the U. S. Oil Pollution Act of 1990 to minimize future
spills include double-hulled ships, tug escort zones for tight
passages, and tanker-free zones for critical areas. To these
might be added minimum training requirements for the
crews. Exxon now employs the following preventive mea-
sures in Prince William Sound.145
Tugs escort tankers.
The U. S. Coast Guard follows traffic with radar.
Reduced speeds are used.
Traffic restrictions are tighter in bad weather.
Better equipment and training have made it safer to miss
icebergs.
A harbor pilot assists navigation.
The use of alcohol and drugs is prohibited and random
testing is done.
In 1991, 235 oil spills were reported in the Port of
Philadelphia, Pennsylvania.146 Canada has 12 spills a day
of which 9 are due to oil.147 A crewman’s mistake on a
tanker released 18,000 gall of tetrachloroethylene into the
shrimp-fishing grounds near Port O’Connor, Texas, in
1996.148
Accidents can be very expensive, not just in plant re-
placement costs, but also compensation to victims (as
well as lost profits from lost sales). When operators at
General Chemical’s Richmond, California, plant over-
heated a railroad tank car, a safety relief valve sent fum-
ing sulfuric acid over the area. More than 20,000 people
sought medical treatment. Five freeways and several
rapid-transit stations closed. A fund of 92.8 million dol-
lars has been set up to compensate the victims.149 A re-
Chapter 1
lease of sulfur trioxide from General Chemical’s Augusta,
Georgia, plant on November 17, 1998, sent 90 people to
the hospital with eye, nose, and lung irritation. This ex-
ceeded a worse-case scenario that had been prepared for
the plant.150 These reagents are often used to make deter-
gents. The use of alkyl polyglycoside detergents, which
are made from sugars and fats, would reduce or eliminate
the need for these reagents.
An October 23, 1992, release of 2.5 tons of unburned
hydrocarbons, mainly butadiene, from an extinguished
flare at an Oxy Chem plant in Corpus Christi, Texas, re-
sulted in an out-of-court settlement of a class action lawsuit
for 65.7 million dollars by nearby residents with health
complaints.151 A jury in New Orleans, Louisiana, awarded
damages of 3.4 billion dollars for a fire that resulted when
a tank car carrying butadiene caught fire in September
1987. The fire caused the evacuation of more than 1000
nearby residents.152 A fire occurred at the University of
Texas on October 19, 1996, destroying a laboratory.153 It
was caused by pouring a solvent into which sodium had
been cut, down the drain, the reaction of remaining traces
of sodium with water igniting the mixture. The six-alarm
fire was the tenth incident in the building which involved
the Austin Fire Department since February 1992. Under
pressure from the Fire Department, the university will
spend 30.2 million dollars to bring the building up to cur-
rent fire safety standards.
More than 44 million Americans live or work near
places that pose risks from the storage or use of dangerous
industrial chemicals.154 The cost of accidents may be more
than just a monetary one to the company. A fire and ex-
plosion occurred on July 4, 1993, in a Sumitomo Chemi-
cal plant in Niihama, Japan, that made over half of all the
epoxy-encapsulation resin for semiconductor chips used in
the entire world. Cutting off the supply would have been a
serious inconvenience to the customers. The company took
the unusual step of letting other companies use its tech-
nology until it could rebuild its own plant, so that a supply
crisis never developed. The company still supplied 50% of
the world’s requirements for that resin in 1999.155
Why do these accidents continue to happen? One critic
says,
Hourly workers struggle to maintain production in
the face of disabled or ignored alarms, undocu-
mented and often uncontrollable bypasses of estab-
lished components, operating levels that exceed de-
sign limits, postponed and severely reduced
turnaround maintenance and increasing maintenance
on ‘hot’ units by untrained, temporary non-union
contract workers.156
Introduction
Another source mentions “institutional realities that under-
cut corporate safety goals, such as incentives that promote
safety violations in the interest of short-term profitability,
shielding upper management from ‘bad news’ and turnover
of management staff.”157 A third says that “Many chemical
plant disasters have been precipitated by an unplanned
change in process, a change in equipment or a change in
personnel.”158
It has been estimated that the U. S. petrochemical in-
dustry could save up to 10 billion dollars/yr by avoiding ab-
normal situations or learning how to better deal with
them.159 A team studying abnormal situations management
identified eight key issues:
Lack of management leadership
The significant role of human errors
Inadequate design of the work environment
Absence of procedures for dealing with abnormal oper-
ations (as opposed to emergencies)
Loss of valuable information from earlier minor
incidents
The potential economic return
Transferability of good abnormal situations perfor-
mance to other plants
The importance of teamwork and job design.
The paper mentions 550 major accidents at U. S. petro-
chemical plants (each with more than 500,000 dollars lost)
in the last 5 years, with 12.9 billion dollars total equipment
damage. Learning from case histories is helpful, but is evi-
dently not enough.160
It is easy to blame accidents on human error, but good
design can often minimize this.161 Avoid poor lighting or
contrast. Provide a checklist so that the operator will find it
easy to recall all of the necessary information. Most valves
have right-handed threads. Do not mix in any that have left-
handed threads. Mount them so that they are easy to access,
and the labels are easy to see.
The state of Delaware has an Extremely Hazardous
Substances Risk Management Act enforced by a two-man
Industrial Disaster Management Group. It does not dis-
courage the use of hazardous substances, but it does require
companies to have good equipment maintenance programs,
written instructions on how to operate the equipment, plus
operator training. The companies must also study how
equipment can fail, how operators can make mistakes, the
probability of human error, and what areas might be af-
fected if an accident occurs.162 The state also has an emer-
gency response team that is always on call.163 Delaware
also proposes to monitor how much toxic pollution state
residents receive at home, at work, and in the air.164 On the
national scale, the U. S. Environmental Protection Agency
11
is setting up a Risk Management Program that will require
users of hazardous chemicals “to publish emergency re-
lease plans, worst-case scenarios and five year accident
histories,” by June 1999.165 Hazardous materials emergen-
cies are covered in a book edited by Cashman.166
New Jersey adopted a Toxic Catastrophe Prevention Act
in 1986, which requires risk assessment by companies.167
The Kanawha Valley Hazardous Assessment Project in
West Virginia developed worst-case scenarios for 12
chemical plants in the area.168 The chemicals studied in-
cluded acrylonitrile, vinylidene chloride, butyl isocyanate,
methylene chloride, chlorine, phosphorus trichloride, hy-
drogen sulfide, methyl isocyanate, phosgene, ethylene ox-
ide, sulfur trioxide, and others
In addition to the amounts of chemicals released to the
environment through accidents, the U. S. Toxic Release In-
ventory shows the release of 2.43 billion lb into air, land, or
water in 1996,169 down from 3.21 billion lb in 1992.170,171
(The data is available on a number of Internet sites, includ-
ing www.epa.gov/opptintr/tri.) The total decline since the
law became effective in 1987 has been 46%. This right-to-
know law was enacted in the aftermath of the Bhopal acci-
dent. It now covers nearly 650 chemicals out of about
72,000 in commerce. (It is credited with causing industries
to reduce emissions more than the usual command-and-
control regulations that can lead to cumbersome, adversar-
ial legal proceedings.172) Facilities are not required to re-
port releases unless they manufacture or process more than
25,000 lb or handle more than 10,000 lb of the chemicals
annually.173 The U. S. Environmental Protection Agency
has proposed lower reporting amounts for some, especially
toxic chemicals (e.g., 10 lb of chlordane [a persistent chlo-
rinated insecticide], polychlorinated biphenyls, or mer-
cury; and 0.1 g dioxins). Some compounds have also been
removed from the list. Acetone (129 million lb, released in
1993) and nonaerosol forms of sulfuric acid (106 million lb
injected underground of 130 million lb, released in 1993)
have been removed from the list recently because they are
not likely to cause adverse effects to the environment or to
human health under conditions of normal use.174 However,
the amount of production-related waste has remained rela-
tively constant at about 37 billion lb since 1991, when data
collection began.175 About 250 million metric tons of haz-
ardous waste is generated each year in the United States.
This is about 1 ton/person.176 The number of Superfund
sites, where toxic waste was deposited in the past and that
now need to be cleaned up, is expected to reach 2000, with
an estimated cost to clean up each site of 26 million
dollars.177
The numbers in the Toxic Release Inventory must not be
taken out of context. Large reductions in the numbers for
hydrogen chloride and sulfuric acid between 1987 and
12
1996 resulted from narrowing the reporting requirements
to cover only airborne releases.178 About half of the major
reductions in the waste generated by an 80-company sam-
ple resulted from redefining on-site recycling activies as in-
process recovery, which does not have to be reported.179 A
change in the production level of a plant can also change
the numbers.
The Toxic Release Inventory for Delaware for
1993–1996 will illustrate how the system works
(Table 1.1).
The large releases from the first two companies were
largely solvents used in painting cars. These might be re-
duced to near zero by use of powder coating for finishing
cars, and cleaning parts with aqueous detergents (see Chap.
8). Part of the reduction by Chrysler may have involved
substitution of a nonreportable solvent for a reportable one
(as suggested by a GM employee.) The big reductions for
both companies stem from major shutdowns to retool for
new models. During this period, Chrysler reduced its use
per unit of production by 6%, whereas GM increased its use
per unit of production by 19%. Included in the Sun Oil re-
leases was 150,000 lb of ethylene oxide. The nylon plant
losses were mainly hydrochloric acid from traces of chlo-
ride in the coal burned to power the plant. The increased re-
leases in 1995–1996 reflect a new requirement to report ni-
trate released by the wastewater treatment plant. A
scrubber could be used to remove the hydrogen chlorine
from the stack gases. The metals company lost primarily
trichloroethylene used in cleaning metal parts. Cleaning
with aqueous detergent could reduce the amount lost to
zero (see Chap. 8). (Elsewhere in Delaware, the town of
Smyrna has to treat its water supply to remove
trichloroethylene before distributing the water to its cus-
tomers.) The releases from Formosa Plastics included
111,000 lb of the carcinogen, vinyl chloride. The substitu-
tion of polyolefins, including those made with new metal-
locene catalysts, for polyvinyl chloride might eliminate the
need to make vinyl chloride. Townsends’ losses were hex-
Table 1.1 Toxic Release Inventory for Delaware (Partial)
Company 1993
Chrysler 987,440
General Motors 826,311
Sun Oil refinery 463,010
duPont Seaford nylon plant 455,900
Star Enterprise refinery 344,549
Camdel Metals 240,005
Formosa Plastics 146,621
Townsends
Chapter 1
ane from the extraction of oil from soybeans. Extraction
with supercritical carbon dioxide would eliminate the need
for hexane (see Chap. 8). Other releases in the state in-
cluded the carcinogens acrylonitrile, benzene,
dichloromethane, and ethylene oxide. For comparison, the
state of Delaware estimates that cars and trucks contribute
138,040 lb/day of volatile organic compounds into the air.
This means that local traffic puts out in 2.5 days what the
Star Enterprise refinery (now Motiva Enterprises) releases
in a year. The poultry industry, in the same county as the
nylon plant, probably releases more nitrates to streams than
the nylon plant (by putting excess manure on fields). The
total emissions in Delaware are less than what some single
companies release in other parts of the nation (e.g., East-
man Chemical, 29 million lb).180
One interesting approach to the loss of volatile liquids is
the use of an evaporation suppressant for the styrene used
to cure unsaturated polyester resins.181 The suppressant,
made from a bisphenol A epoxy resin, stearic acid,
colophony, triethanolamine, glycerol monostearate, cal-
cium stearate, and sorbitan monostearate, may coat the sur-
face to retard evaporation.
Chemicals in lakes and streams caused 46 states to issue
public health warnings to avoid or curtail the eating of fish.
Mercury was the cause in 60% of the cases, polychlori-
nated biphenyls 22%, chlordane (a banned chlorinated in-
secticide) 7%, DDT 2%, the remainder being spread over
25 chemicals.182 Fish advisories went up 26% from 1995 to
1996 to the point where 15% of the lakes and 5% of the
rivers in the United States are now covered.183 In fairness
to industry, it should be pointed out that a study by the
Lindsay Museum, in Walnut Creek, California, found that
70% of the chemicals in San Francisco Bay came from the
daily activities of ordinary people (e.g., oil from leaky cars,
copper dust from brake pads, garden fertilizers, and pesti-
cides).184 Nearly 50% of the oil in the world’s waters
comes from people carelessly discarding used oil on the
ground or down drains.185 Sixty-six percent of Delaware
Pounds released by year
1994 1995 1996
652,146 399,918 105,655
1,285,570 995,747 581,039
120,280 147,200 92,500
502,687 774,488 654,970
292,758 195,007 162,642
92,000 10,740 7,020
151,499 149,211 132,862
532,278 500,154
Introduction
rivers and streams do not meet minimum standards for
swimming, and 29% do not support normal aquatic life.186
Occupational illness and injury187 cost 30–40 billion
dollars/yr in the United States.188 In 1994 there were 6.8
million injuries and illnesses in private industry, amounting
to 8.4 cases per 100 workers. Nearly two-thirds were dis-
orders associated with repeated trauma, such as carpal tun-
nel syndrome.189 The Occupational Safety and Health Act
of 1970 set up the National Institute Safety and Health
(NIOSH) to study the problem and the Occupational Safety
and Health Administration (OSHA) to deal with it through
inspections and regulations. Both have received so much
criticism of their effectiveness that they are struggling to
find more effective ways to deal with the problem.190
NIOSH is searching for practical ways to protect workers,
especially those in small businesses from methylene chlo-
ride, tetrachloroethylene, diesel exhaust in coal mines, iso-
cyanates, 2-methoxyethanol, and others. OSHA is about to
expand a plan that worked well in Maine, a state that used
to have one of the worst accident and illness records in the
United States.191 The 200 firms with the worst records
were asked to look for deficiencies and to correct them.
They were also inspected. These measures cut injuries and
illnesses over a 2-year period.
IV. WASTE AND ITS MINIMIZATION
Nearly everything made in the laboratory ends up as waste.
After the materials are made, characterized, and tested,
they may be stored for a while, but eventually they are dis-
carded. In schools, the trend is to run experiments on a
much smaller scale, which means that less material has to
be purchased and less waste results.192 (Even less material
will be used if chemistry-on-a-chip becomes common-
place.193) Two things limit how small a scale industrial
chemists can use. One is the relatively large amount of a
polymer needed for fabrication of molded pieces for testing
of the physical properties. There is a need to develop
smaller-scale tests that will give data that is just as good.
The second factor is the tendency of salesmen to be gener-
ous in offering samples for testing by potential customers.
A lot of the sample received by the potential customer may
never be used.
Some industrial wastes result because it is cheaper to
buy new material than to reclaim the used material. Some
catalysts fall in this category. The 1996 American Chemi-
cal Society National Chemical Technician Award went to a
technician at Eastman Chemical who set up a program for
recovering cobalt, copper, and nickel from spent catalysts
for use by the steel industry.194 This process for avoiding
landfill disposal gave Eastman significant savings. Some
13
waste metal salts can be put into fertilizer as trace elements
essential for plant growth. However, this practice has been
abused in some cases by putting in toxic waste (e.g., some
that contain dioxins and heavy metals).195 Even a waste as
cheap as sodium chloride can be converted back to the
sodium hydroxide and hydrochloric acid that it may have
come from, by electrodialysis using bipolar membranes.196
(Membrane separations are covered in Chap. 7). Waste
acid can be recovered by vacuum distillation in equipment
made of fluoropolymers.197
Mixed solvents can be difficult to recover. If they are
kept separate, they can be reclaimed by distillation on site.
The capital investment required is paid back by the reduced
need to buy new solvent. In Germany “completely en-
closed vapor cleaners” give 99% reduction in solvent emis-
sions.198 After cleaning and draining, the air-tight chamber
is evacuated, the solvent vapors are captured by chilling
and adsorption on carbon. When a sensor shows that the
solvent is down to 1 g/m3 the vacuum is released so that the
lid can be opened.
In some cases the amount of waste may be considered
too small to justify the research needed to find a use for it
or to improve the process to eliminate it. The staff may also
be so busy with potentially profitable new ventures that it
hesitates to take time to devise a new process for a mature
product made in an established plant. This may be particu-
larly true in the current period of downsizing and
restructuring.
Improved process design can minimize waste. Deborah
Luper suggests asking the following questions:199
Are you using raw materials that are the target of com-
pound-specific regulations?
Can carriers and solvents be eliminated, reduced, or re-
cycled?
Can you find riches in someone else’s wastes?
Are there riches in your wastes?
Where does the product end up after use and what hap-
pens to its components?
What percentage of the incoming materials leave the
plant in the finished products?
What support equipment and processes generate waste?
How long is the waste treatment train?
Can process water be recycled?
What can be achieved with better process control?
Improved housekeeping can often lead to reduced emis-
sions and waste.200 The leaky valves and seals can be fixed
or they can be replaced with new designs that minimize
emissions.201 These include diaphragm valves, double me-
chanical seals with interstitial barrier liquids, magnetic
drives, better valve packings, filled fabric seals for floating
roof tanks, and so on. Older plants may have some of the
14
worst problems.202 The U. S. Environmental Protection
Agency fined Eastman Kodak 8 million dollars for organic
solvents leaking from the 31 miles of industrial sewers at
its Rochester, New York, plant. This emphasizes the need
for regular inspections and preventive maintenance, which
in the long run is the cheapest method. Vessels with smooth
interiors lined with non- or low-stick poly(tetrafluoroethy-
lene) can be selected for batch tanks that require frequent
cleaning. These might be cleaned with high-pressure water
jets instead of solvents. Perhaps a vessel can be dedicated
Figure 1.1 (Reprinted from Chem. Eng. News, Oct 24, 1994, with permission of E. I. duPont de Nemours & Co., Inc.)
Chapter 1
to a single product, instead of several, so that it does not
have to be cleaned as often. If a product requires several
rinses, the last one can be used as the first one for a new lot
of product. Volatile organic compounds can be loaded with
dip tubes instead of splash loading. Exxon has used such
methods to cut emissions of volatile organic compounds by
50% since 1990.203 Install automatic high-level shut-offs
on tanks. Use wooden pallets over again, instead of con-
sidering them as throw-away items. The current ethic
should be reduce, reuse, and recycle in that order.
Introduction
1.15
A waste is not a waste if it can be reused. For example,
one steel manufacturer drops pickle liquor down a 100-
ft–tall tower at 1200°F to recover iron oxide for magnetic
oxide and hydrogen chloride for use again in pickle
liquor.204 The pomace left over from processing pears and
kiwis can be dried and used to increase the dietary fiber in
other foods.205 Food-processing wastes and wastes from
biocatalytic processes often become feed for animals. A re-
finery stream of ethane, methane, butane, and propane, that
was formerly flared as waste, will be processed to recover
propane for conversion to propylene, then to polypropy-
lene.206 Organic chemical wastes may end up as fuel for the
site’s power plant or for a cement kiln, but more valuable
uses would be preferable. Waste exchanges are being set
up. One company’s waste may be another’s raw material.
For example, calcium sulfate from flue gas desulfurization
in Denmark and Japan, but not in the United States, ends up
in dry wall for houses. If the waste exchange merely pairs
up an acid and a base so the two can be neutralized, rather
than reclaimed, the result is waste salts. Admittedly, these
are probably not as toxic as the starting acid and base, but
they still have to be disposed of somewhere. Several gen-
eral references on waste minimization and pollution pre-
vention are available.207
On-line continuous monitoring of reactions can reduce
waste by better control of the reaction and elimination of
many laboratory samples that are discarded later. This can
be used in the laboratory to replace analyses by thin-layer
1.16
15
chromatography. For example, an infrared probe was used
to monitor a copolymerization of 2-ethylhexyl acrylate
and styrene in an aqueous emulsion.208 The yield in or-
ganic reactions is seldom 100%. If uses can be found for
the by-products, then everything can be sold for more
than the fuel value of the by-products. There may still be
problems if the market sizes for the various products do
not fit the volumes produced or that can be produced in a
slightly altered process. A few examples of upgrading
will be given.
Dimethyl terephthalate for the production of poly(ethy-
lene terephthalate) is produced by the cobalt salt-cat-
alyzed oxidation of p-xylene with oxygen (reaction
1.15).209 In this free radical process, some biphenyl
derivatives are formed. In addition, triesters are formed
from any trimethylbenzenes in the feed. Thus, the still
bottoms contain several compounds, which are all methyl
esters. Hercules found that transesterification of this mix-
ture with ethylene glycol led to a mixture of polyols that
could be used with isocyanates to form rigid
polyurethanes. For the price, the “Terate” product was
hard to beat.
duPont markets a number of intermediates from its
manufacture of fibers,210 as shown by the accompanying
advertisment often seen in Chemical Engineering News in
1994 (Fig. 1.1). Adipic acid is prepared by oxidation of a
mixture of cyclohexanol and cyclohexanone obtained, in
turn, by the oxidation of cyclohexane (reaction 1.16).211
Unfortunately, this process produces undesired nitro-
gen oxides at the same time. Some shorter dibasic acids
are also formed. Trimerization of 1,3-butadiene is used to
prepare 1,5,9-cyclododecatriene, an intermediate for an-
other nylon.212 In the process, 1,5-cyclooctadiene and 4-
vinylcyclohexene are formed as by-products (reaction
1.17).
The hexamethylenediamine used with adipic acid to
make nylon-6,6 is made by reduction of adiponitrile, pre-
pared, in turn, by the addition of hydrogen cyanide to 1,3-
butadiene (reaction 1.18).213
An earlier process that did not use the toxic hydrogen
cyanide was discarded because it produced more waste
16
1.17
than the HCN route. In it, the adiponitrile was made by the
heating amonium adipate (see reaction 1.19).
The 2-pentenenitrile, 2-methyl-3-butenenitrile, and
methylglutaronitrile in Figure 1.1 are by-products of this
reaction sequence. duPont is still studying the phosphines
used as ligands for the nickel in an effort to find one
bulky enough to favor terminal addition only.214 Reduc-
tion of the various nitriles leads to the amines in Figure
1.1, including the cyclic ones. The 2,3-dichloro-1,3-buta-
diene is probably a by-product in the synthesis of 2-
chloro-1,3-butadiene used to make Neoprene rubber.
duPont also polymerizes acrylonitrile to prepare
poly(acrylonitrile) fiber (Orlon). Acetonitrile is obtained
as a by-product of the ammoxidation of propylene to pro-
duce acrylonitrile (reaction 1.20).
Paul V. Tebo has described a duPont goal of zero emis-
sions and zero waste.215
The hydroformylation of propene to form butyralde-
hyde invariably produces some isobutyraldehyde at the
same time (reaction 1.21).216 One of the best processes uses
a water-soluble rhodium phosphine complex to produce
94.5% of the former and 4.5% of the latter.217 The products
form a separate layer that is separated from the water.
Rhodium is expensive so it is important to lose as little as
possible. In 10 years of operation by Rhone-
Poulenc–Ruhrchemie 2 million metric tons of butyralde-
hyde have been made with the loss of only 2 kg of rhodium.
The process is 10% cheaper than the usual one. Higher
olefins are not soluble enough in water to work well in the
process. The process does work for omega-alkenecar-
boxylic acids such as 10-undecenoic acid, where a 97:3
1.18
Chapter 1
normal/isoformyl compound is obtained in 99% conver-
sion.218 For higher alkenecarboxylic acids a phase transfer
catalyst, such as dodecyltrimethylammonium bromide
must be used. However, this lowers the normal/iso ratio.
(Chap. 8 contains more on biphasic reactions.)
Over the years a variety of uses have been found for the
isobutyraldehyde by Eastman Chemical and others.219 It is
converted to isobutyl alcohol, neopentyl glycol, isobutyl
acetate, isobutyric acid, isobutylidenediurea, methyli-
soamyl ketone, and various hydrogenation and esterifica-
tion products (1.22).
Neopentyl glycol is used in the preparation of
polyesters. Because there are no -hydrogen atoms, the
polymers are more stable. The self-condensation of isobu-
tyraldehyde followed by reduction leads to 2,2,4-trimethyl-
1,3-pentanediol, the monoisobutyrate of which is the most
common coalescing agent (used at 0.5–2 vol%) in latex
paints. Isobutyl acetate is used as a solvent for nitrocellu-
lose coatings.
Isobutylidenediurea is used as a slow-release fertilizer.
If there is a surplus of isobutyraldehyde, recent work has
shown that it can be decarbonylated to propylene over a
palladium on silica catalyst.220 There is also the possibility
of dehydrogenation to methacrolein for conversion to
methacrylic acid, then to methyl methacrylate. Dehydra-
tion of isobutyl alcohol would produce isobutylene for con-
version to methyl-tert-butyl ether, although this would
probably be uneconomical.
Uses have been found for 2-methyl-1,3-propanediol (a
by-product of the preparation of 1,4-butanediol) in the per-
sonal care industry.221
Introduction 17

1.19

1.20

1.21

1.22
18
1.23
The preparation of rayon (regenerated cellulose) by the
viscose process222 is being phased out, owing to the envi-
ronmental pollution of the process.
cell-OH  CS2  NaOH →
 (1.1)
cell-OCSSNa →
H
cell-OH  Na
In the new process (1.1), a solution of cellulose in N-
methylmorpholine-N-oxide (1.23) is run into water to pro-
duce the fibers.223 The solvent is recovered, so that there is
no waste. The process not only eliminates the very
flammable and odorous carbon disulfide, but also produces
a much stronger fiber because the degradation of the
molecular weight of the viscose process is avoided.
V. CONCLUSIONS
The challenge is to reduce the incidence and severity of ac-
cidents, waste, the toxicity of chemicals, and the amount of
energy used, while still providing the goods that society
needs. Several recent provocative papers suggest some
ways to do this.224 The key is in the preparation of more so-
phisticated catalysts. Thus, solid acids may be able to re-
place the risky hydrogen fluoride and sulfuric acid used in
alkylation reactions in the refining of petroleum. Zeolites
offer the promise of higher yields through size and shape
selectivity (see Chap. 6). With the proper catalysts, oxida-
tions with air and hydrogen peroxide may replace heavy
metal-containing oxidants (see Chap. 4). Enantioselective
catalysis may allow the preparation of the biologically ac-
tive optical isomer without the unwanted one (see Chap.
10). It may be possible to run the reaction in water at or near
room temperature using biocatalysis instead of in a solvent
or at high temperature (see Chap. 9). Some processes yield
more by-product salts than the desired product. Sheldon225
recommends a salt-free diet by improved catalytic meth-
ods. These and other possibilities will be examined in the
chapters that follow.
Bodor has suggested the design of biologically safer
chemicals through retrometabolic design.226 As an exam-
ple, the ethylene glycol used widely as an antifreeze in cars
Chapter 1
might be replaced with less hazardous propylene glycol.
The former is converted by the body to glycolaldehyde,
glyoxylic acid, and oxalic acid (1.2), whereas the latter
gives the normal body metabolites lactic acid and pyruvic
acid (1.3).227
A lethal dose of ethylene glycol for man is 1.4 mL/kg.
Its problem is that its sweet taste makes it attractive to chil-
dren and pets. An alternative approach is to add a bittering
agent to it. The estimated lethal dose of propylene glycol
for man is 7 mL/kg.
The U. S. National Science and Technology Council has
laid out a research and development strategy for toxic sub-
stances and waste.228 Hirschhorn has suggested ways to
achieve prosperity without pollution.229
Two examples will indicate improvements that have
come about by simple economics of the marketplace.
Olefins higher than ethylene are usually converted to the
epoxides indirectly by adding hypochlorous acid, then base
to split out hydrogen choride (1.24). However, an Arco
process does this without formation of by-product salt.230
Dow is switching to the new route.231
The hydroperoxide formed by the air oxidation of ethyl-
benzene is used to convert propylene to its oxide. The by-
product 1-phenylethanol is dehydrated to styrene, a second
valuable product. The disadvantage of such a process is
that the demand for such products has to be equal on a mo-
lar basis.
Propylene used to be converted to isotactic polypropy-
lene with titanium tetrachloride and diethylaluminum
chloride in a hydrocarbon solvent. The atactic polypropy-
lene obtained by evaporation of the solvent after filtration
of the desired isotactic polymer was of little value, some
going into adhesives. An acidic deashing step was neces-
sary to remove residual titanium, aluminum, and chloride
from the polymer, the metal-containing residues ending
up in a landfill. This process was supplanted by high-
mileage catalysts during which the titanium chloride was
supported on magnesium chloride. These were activated
by triethylaluminum in the presence of ligands that en-
hance the stereoselectivity of the catalysts. The result was
a product that required no deashing and no removal of at-
actic polymer. In the next step in the evolution, the sol-
vent was eliminated by polymerization in the gas phase or
in liquid propylene. By the proper choice of catalyst, the
polymer can be obtained in large enough granules so that
the older practice of extruding molten polymer to form a
strand that was chopped into “molding powder” is no
longer necessary. The field is still evolving. Metallocene
single-site catalysts232 allow greater control of the product
(1.2)
Introduction
1.24
and have led to new products. Ethylene--olefin copoly-
mers can be made from ethylene alone, the -olefin being
made in situ. Ways are now available to prepare syndio-
tactic polypropylene in a practical way. A new polypropy-
lene made with such catalysts may be able to supply the
properties now found only in plasticized polyvinyl chlo-
ride. To make the products even greener, consumer use
must be reduced, the low level of reuse and recycle must
be raised, and a renewable source of the propylene, rather
than petroleum, must be used. Propylene could be made
by reduction, then dehydration of acetone from fermenta-
tion (see Chaps. 12 and 14).
Hirschhorn233 feels that “An environmentally driven in-
dustrial revolution is beginning.” Brian Rushton, president
of the American Chemical Society in 1995, said that
We will gradually eliminate environmentally un-
sound processes and practices from our industry. We
will build a better environment to work and live in.
We will keep scientists and engineers both employed
and at the cutting edge of technology as they serve
the competitive needs of the nation. Last but by no
means least, we will create a better image for chem-
istry and the profession.234
Lastly, Gro Harlem Brundtland, head of the World
Health Organization and former prime minister of Norway
and the secretary general of the World Commission on En-
vironment and Development has noted that “The obstacles
to sustainability are not mainly technical. They are social,
institutional and political.”
VI. SUMMARY OF SOME IMPORTANT
POINTS
1. Scientists may not be able to anticipate the influ-
ence of their work on society.
19
(1.3)
2. Chemophobia is rampant at the same time that the
real risks are often unappreciated.
3. “Natural” is often misinterpreted.
4. In the United States, oversight of herbal remedies
and dietary supplements by the Food and Drug
Administration would be desirable.
5. Chemical accidents will continue to happen. Hu-
man error will often be the cause. If the chemicals
being used were nontoxic, the severity of the acci-
dents would be reduced greatly.
6. The Toxic Release Inventory is proving to be a
good way to encourage voluntary reductions of
emissions.
7. A waste is not a waste if a valuable use can be
found for it. However, it is better to find a better
process that eliminates the waste.
8. While improved housekeeping can reduce re-
leases, it is better to choose a new process with be-
nign reagents.
9. If you do not use it, you cannot lose it, you do not
have to buy it and you do not have to treat it for
disposal.
10. Green chemistry and sustainability are intertwined
with the social and political fabric of the country
and cannot be considered in isolation.
11. Green chemistry need not be more expensive. Pol-
lution prevention is often cheaper than end-of-the-
pipe treatments. Rethinking the entire process can
often be helpful.
12. The problems are not all elsewhere.
13. There may be a hierarchy of approaches to the
problem from the least change to the most change.
14. Be patient, since it may take a while to work the
bugs out of the new process.
15. An expensive catalyst is not too expensive if none
is lost. The lowest price per unit of performance is
20
what counts. This must include all costs, even the
diffuse costs of emissions.
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Introduction
Plant Disasters, Gulf Publishing, Houston, 1994; (b) Loss
Prevention, vol. 18, American Institute Chemical Engi-
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180. Delaware Department of Natural Resources and Environ-
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186. C.A.G. Tulou, Outdoor Delaware, 1998, 7(1), 2.
187. L. diBerardinis, ed., Handbook of Occupational Safety and
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188. B. Hileman, Chem. Eng. News, Mar. 4, 1996, 16; May 6,
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189. Chem. Eng. News, Jan. 22, 1996, 17.
190. D.J. Shanefield, Chem. Eng. News, Oct. 23, 1995, 4.
191. (a) R. Zanetti, Chem. Eng., 1995, 102(10), 5; (b) D. Han-
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192. (a) D. Mayo, R.M. Pike and P.K. Trumper, Microscale Or-
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1994; (b) M.M. Singh, R.M. Pike, and Z. Szafran. General
Chemistry Micro- and Macroscale Laboratory, John Wiley
& Sons, New York, 1994; (c) M.M. Singh, K.C. Swallow,
R.M. Pike, and Z. Szafran, J. Chem. Ed., 1993, 70, A39; (d)
M.M. Singh, R.M. Pike, and Z. Szafran, Preprints A.C.S.
Div. Environ. Chem., 1994, 34(2). 194; (e) Z. Szafran, R.M.
Pike, and J.C. Foster, Microscale General Chemistry Lab-
oratory with Selected Macroscale Experiments, Wiley,
New York, 1993; (f) Z. Szafran, R.M. Pike, and M.M.
Singh, Microscale Inorganic Chemistry: A Comprehensive
Laboratory Experience, Wiley, New York, 1991; (g) J.L.
Skinner, Microscale Chemistry—Experiments in Minia-
ture, Royal Soc. Chem., Cambridge, UK, 1998.
193. M. Freemantle, Chem. Eng. News, Feb. 22, 1999, 27.
194. Chem. Eng. News, June 3, 1996.
195. Chem. Eng. News, Mar. 30, 1998, 29.
196. S. Mazrou, H. Kerdjoudj, A.T. Cherif, A. Elmidaoui, and
J. Molenat, New J. Chem., 1998, 22, 355.
197. Environ. Sci. Technol., 1998, 32, 119A.
198. “Guide to Cleaner Technologies—Cleaning and Degreas-
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199. D. Luper, Chem. Eng. Prog., 1966; 92(6), 58.
200. (a) N. Chadha, Chem. Eng. Prog., 1994, 90(11), 32; (b) Of-
fice of Technology Assessment, Industry, Technology and
the Environment: Competitive Challenges and Business
Opportunities, Washington, D.C., 1994, Chap. 8; (c) K.
Martin and T.W. Bastock, eds., Waste Minimisation: A
Chemist’s Approach, Royal Society of Chemistry, Cam-
bridge, 1994; (d) J.H. Siegell, Chem. Eng., 103(6). 92; (e)
M. Venkatesh and C.W. Moores, Chem. Eng. Prog., 1998,
94(11), 26; (f) S.B. Billatos and N.A. Basaly, Green Tech-
nology and Design for the Environment, Taylor and Fran-
cis, Washington, D.C., 1997; (g) M. Venkatesh, Chem.
Eng. Prog., 1997, 93(5), 33. (h) P. Crumpler, Chem. Eng.,
1997, 104(10), 102.
201. (a) K. Fouhy, Chem. Eng., 1995, 102(1), 41; (b) J. Jarosch,
Chem. Eng., 1996, 103(5), 120; (c) Chem. Eng., 1996,
103(5), 127; (d) D.M. Carr, Chem. Eng., 1995, 102(8), 78;
(e) B.J. Netzel, Chem. Eng., 1995, 102(8), 82B; (f) Chem.
Eng., 1995, 102(11); (g) C. Brown and P. Dixon, Chem.
Eng. Prog., 1996, 92, 42; (h) J.H. Siegell, Chem. Eng.
Prog., 1998, 94(11), 33.
202. E.M. Kirschner, Chem. Eng. News, July 10, 1995, 14.
203. Environmental, Health and Safety Progress Report for
1995, Exxon Corp., 1996, p 11.
204. J. Szekely and G. Trapaga, Technol Rev., 1995, 98(1), 30.
205. M.A. Martin-Cabrejas, R.M. Esteban, F.J. Lopez-Andreu,
K. Waldron, and R.R. Selvendran, J. Agric. Food Chem.,
1995, 43, 662.
206. M. Reisch, Chem. Eng. News, Feb. 10, 1997, 9.
207. (a) B. Crittenden and Kolaczkowski, Waste Minimization
Guide. Inst. Chem. Eng., 1994; (b) D.F. Ciambrone, Waste
Minimization as a Strategic Weapon, Lewis Publishers,
Boca Raton, Florida, 1995; (c) T.E. Higgins. Pollution
Prevention Handbook. Lewis Publishers, Boca Raton,
Florida, 1995; (d) D.T. Allen, Adv. Chem. Eng., 1994, 19,
24
251; (e) L. Theodore, Pollution Prevention, van Nos-
trand–Reinhold, New York, 1992; (f) L. Theodore, Pollu-
tion Prevention—Problems and Solutions. Gordon and
Breach, Reading, UK, 1994; (g) M.J. Healy, Pollution Pre-
vention Opportunity Assessments—A Practical Guide, Wi-
ley, New York, 1998; (h) G.F. Nalven, Practical Engi-
neering Perspectives—Environmental Management and
Pollution Prevention, American Institute of Chemical En-
gineers, New York, 1997; (i) D.T. Allen and K.S. Ross,
Pollution Prevention for Chemical Processes. Wiley, New
York, 1997; (j) J.H. Clark, ed., Chemistry of Waste Min-
imisation, Blackie, London, 1995; (k) EPA. Pollution Pre-
vention Guidance Manual for the Dye Manufacturing In-
dustry, U.S. Environmental Protection Agency,
EPA/741/B-92-001.
208. (a) E.G. Chatzi, O. Kammona, and C. Kiparissides, J.
Appl. Polym. Chem., 1997, 63, 799; (b) Such probes are
available commercially, e.g., from ASI Applied Systems,
Annapolis, Maryland.
209. K. Weissermel and H–J. Arpe. Industrial Organic Chem-
istry, 2nd ed., VCH, Weinheim, 1993, pp 388–390.
210. (a) L.E. Manzer in P.T. Anastas and C.A. Farris, Benign By
Design: Alternative Synthetic Design for Pollution Preven-
tion, ACS Symp. 577, Washington, D.C., 1994, pp
146–147; (b) M. Joucla, P. Marion, P. Grenouillet, and J.
Jenck in J.R. Kosak, and T.A. Johnson, eds. Catalysis of Or-
ganic Reactions. Marcel Dekker, New York, 1994, p. 127.
211. K. Weissermel and H–J. Arpe, Industrial Organic Chem-
istry, 2nd ed., VCH, Weinheim, 1993, pp 238–239.
212. K. Weissermel and H–J. Arpe, Industrial Organic Chem-
istry, 2nd ed., VCH, Weinheim, 1993, pp 241–242.
213. K. Weissermel, H–J. Arpe, Industrial Organic Chemistry,
2nd ed., VCH, Weinheim, 1993, pp 244–245.
214. K.A. Kreutzer and W. Tam, Chem Abstr 1996, 124,
118251, 147112.
215. (a) J.H. Krieger, Chem. Eng. News, July 8, 1996, 12; (b)
P.V. Tebo, Chemtech, 1998, 28(3), 8.
216. K. Weissermel and H–J. Arpe, Industrial Organic Chem-
istry, 2nd ed., VCH, Weinheim, 1993, pp 127–131.
217. B. Cornils and E. Wiebus, Chemtech, 1995, 25(1), 33.
218. B. Fell, C. Schobben, and G. Papadogianakis, J. Mol.
Catal., A: Chem., 1995, 101, 179.
219. (a) SRI International, Chemical Economics Handbook. Jan
1991, under oxo chemicals; (b) H. Bach, R. Gartner, and B.
Cornils, Ullmann’s Encyclopedia Industrial Chemistry,
5th ed. 1985, A4, pp. 450–452.
220. R. Song, D. Ostgard, and G.V. Smith. In: W.E. Pascoe, ed.,
Catalysis of Organic Reactions. Marcel Dekker, New
York, 1992.
221. E.M. Kirschner, Chem.Eng. News, July 1, 1996, 18.
222. A. Turbak, Encyclopedia of Polymer Science and Engi-
neering, 2nd ed., 1988, 14, 45.
223. (a) M. Hirami, J. Macromol Sci. Pure Appl. Chem., 1996,
A33, 1825; (b) C. O’Driscoll, Chem. Br., 1996, 32(12), 27;
(c) G. Parkinson, Chem. Eng., 1996, 103(10), 19; (d) S.
Dobson, Chem. Ind. (London), 1995, 870.
Chapter 1
224. (a) R.A. Sheldon, Chemtech, 1994, 24(3), 38; (b) C.B.
Dartt and M.E. Davis, Ind. Eng. Chem. Res. 1994, 33,
2887; (c) J.A. Cusumano, Chemtech., 1992, 22(8), 482;
Appl. Catal. A General, 1994, 113, 181; (d) J. Haber, Pure
Appl. Chem., 1994, 66, 1597; (e) A. Mittelman and D. Lin,
Chem. Ind. (London), 1995, 694.
225. R.A. Sheldon, Chemtech, 1994, 24(3), 38.
226. (a) N. Bodor, Chemtech, 1995, 25(10), 22; N. Bodor. In:
S.C. de Vito, and R.L. Garrett, eds., Designing Safer
Chemicals: Green Chemistry for Pollution Prevention.
ACS Symp 640, Washington, DC, 1996; (b) See also, S.C.
de Vito, Chemtech, 1996, 26(11), 34 for more ways to de-
sign safer chemicals.
227. L.J. Casarett and J. Doull, eds., Toxicology—The Basic
Science of Poisons, Macmillan, New York, 1975, pp. 195,
514, 516, 720.
228. National Science and Technology Council, A National R
& D Strategy for Toxic Substances and Hazardous and
Solid Waste. Sept. 1995, available from U.S. EPA, Office
of Research and Development, Washington, D.C. 20460.
229. J.S. Hirschhorn. Prosperity Without Pollution, van Nos-
trand–Reinhold, New York, 1991.
230. K. Weissermel and H.-J. Arpe, Industrial Organic Chemi-
cals, 2nd ed., VCH, Weinheim, 1993, pp 265–267.
231. M. McCoy, Chem. Eng. News, 1998; Aug. 3: 20.
232. (a) A.M. Thayer, Chem. Eng. News, Sept. 11, 1995, 15; (b)
W.J. Gautier, J.F. Corrigan, N.J. Taylor and S. Collins,
Macromolecules, 1995, 28, 3771, 3779; (c) A. Batistini,
Macromol. Symp., 1995; 100, 137; (d) J. Chowdhury, K.
Fouhy, and A. Shanley, Chem. Eng., 1996, 103(2), 35; (e)
T. Shiomura, M. Kohno, N. Inoue, T. Asanuma, R. Sugi-
moto, T. Iwatani, O. Uchida, S. Kimura, S. Harima, H.
Zenkoh, and E. Tanaka, Macromol. Symp., 1996, 101, 289.
233. J.S. Hirschhorn, Chemtech, 1995, 25(4), 6.
234. B.M. Rushton, Chem. Eng. News, Jan. 2, 1995, 2.
235. X. Zang, E.K. Fubuda and J.D. Rosen, J. Agric. Food
Chem. 1997, 45, 1758.
It would also be good to read all or most of the following be-
fore finishing this book:
K. Martin, T.W. Bastock. Waste Minimisation: A Chemist’s
Approach. Royal Society, Cambridge, UK, 1994.
A. Johansson. Clean Technology. Lewis Publishers, Boca Ra-
ton, FL, 1992.
For additional reading on a sustainable future see:
D.H. Meadows, D.L. Meadows, J. Randers. Beyond the Limits:
Confronting Global Collapse, Envisioning a Sustainable Future,
Chelsea Green Publishers, Mills, VT, 1992.
J.S. Hirschhorn. Chemtech 1995; 25(4):6.
World Commission on Environment and Development. Our
Common Future. Oxford University Press, Oxford, UK, 1987.
G.G. Lebel, H. Kane. Sustainable Development: A Guide to
Our Common Future—The Report of the World Commission on
Environment and Development. Global Tomorrow Coalition,
Washington, DC, 1989.
Introduction
RECOMMENDED READING
1. Waste Minimization
D.T. Allen, Adv. Chem. Eng., 1994, 19, pp. 251–289,
304–312,318–323.
N. Chadha. Chem Eng Prog 1994; 90(11):32.
D. Luper. Chem Eng Prog 1996; 92(6):58.
2. Safer Chemicals and Pollution Prevention
R.A. Sheldon. Chemtech 1994; 24(3):38.
J.A. Cusumano. J Chem Ed 1995; 72:959; Chemtech
1992; 22(8):482.
C.B. Dartt, M.E. Davis. Ind Eng Chem Res 1994;
33:2887.
3. Carcinogens in Foods
B.N. Ames, L.S. Gold. Science 1992; 258:261; Angew
Chem Int Ed Engl 1990; 29:1197.
4. Alternative Medicine
M. Angell, J.P. Kassirer. N Engl J Med 1998; 339:839.
5. Ecology of Increasing Disease
10.
D. Pimentel, M.L. Tort, L.D’Anna, A. Krawic, J.
Berger, J. Rossman, F. Mugo, N. Doon, M. Shriberg,
11.
E. Howard, S. Lee, and J. Talbot. BioScience 1998;
48:817.
12.
EXERCISES
1. Check the companies in your area in the Toxic Re-
lease Inventory (or a comparable compilation; see
preface for Web sites) Compare their releases with
25
comparable companies in other areas. Can you de-
vise ways in which the releases might be reduced?
Could an alternative process eliminate the release
altogether? If possible, visit one of the plants and
see what the employees tell you about possible re-
duction of the releases.
2. Do you look at nuclear energy as a way to avert
global warming or as a potential problem?
3. Are the Environmental Protection Agency and the
Food and Drug Administration (or comparable
agencies in your country) impediments to progress
or our guardians? Are they antiquated and
unrealistic?
4. Check a year of Chem Eng News, Chem Ind
(Lond), or other chemical news magazine for fires,
explosions, spills, and other accidents.
5. Were there any fires, explosions, spills and acci-
dents in your laboratory last year? If so, who
goofed on what?
6. Do you contribute to air and water pollution?
7. Are there any Superfund or comparable sites near
you? If so, what led to them?
8. How do you feel about the use of tobacco, alcohol,
salt, chemical pesticides, and being overweight
and sedentary?
9. Should herbal teas, alternative medicines, and
health food supplements be regulated by the
government?
Do oil spills heal quickly or is there a long-term ef-
fect on nature?
Should all rivers and lakes be fishable and
swimmable?
Pick out some wastes of industry that have often
been pollutants. How could they have been
avoided or made into useful products? If you have
trouble finding some, try lignin, fly ash, “red mud”
(a waste from refining aluminum ore), spent sulfu-
ric acid, chicken feathers, nitrogen oxides from
making nylon, or calcium sulfite from scrubbing
stack gases.
2
Doing Without Phosgene
I. INTRODUCTION
The chemicals used as reagents are often highly reactive
and are used because they are. As such, they may react
readily with components of the human body, such as water,
or the hydroxyl and amino groups of proteins and nucleic
acids. The next chapters will deal with efforts to replace
these toxic materials with inherently safer chemistry. It
may not be possible to replace them completely. This leads
to a hierarchy of approaches (a tiered approach follows),
from the least change to the most change:
No change: Those using the process are confident that
they can handle it. They may not have had any acci-
dents recently.
Go to a closed system and carefully avoid leaks.
Do not ship the chemical or store it in quantity. Prefer-
ably, generate it on site in situ as needed.
Farm out the work to specialist companies that are ex-
perienced in handling it and are willing to do custom
syntheses.
Replace the reagent with a less, but still toxic, reagent
that may be easier to handle.
Replace the reagent with a nontoxic reagent.
Make the product by a different route, using nontoxic
reagents.
Substitute other products for the ones made with the
toxic reagent, preferably ones based on renewable
natural resources.
Ask whether the use is really necessary at all [e.g.,
drinking a 10% solution of sugar in water from a
poly(ethylene terephthalate) soda bottle instead of
just going to a water fountain].
Ban or tax the reagent or the use. Tetraethyllead, for-
merly used as an antiknock agent in gasoline, was
27
banned when the effect on children’s IQ was found.
Chlorofluorocarbons are taxed, as well as being
phased out, because they destroy the ozone layer.
This scheme will be applied to phosgene (bp 7.56°C.),1
a reagent that is made by the reaction of carbon monoxide
with chlorine (2.1) over activated carbon at elevated tem-
peratures.2
CO  Cl2 → COCl2 ( 2.1)
Both the reagents and the product are quite toxic. Phosgene
was used as a war gas in World War I. It causes irritation of
the eyes and nose at 3 ppm or more. The effects are insidi-
ous because the major discomfort comes not at first, but
later. Current practice is to use it in closed systems and not
to store or ship it. Workers wear indicator film badges to
monitor their exposure and to alert them to danger. Custom
phosgenations are offered by PPG Industries3, Hatco4,
Rhone–Poulenc,5 and SNPE6. SNPE has a plant that makes
the phosgene as needed, so that at any one time only a few
kilograms are present in the reactor and piping, an amount
that can be handled by a scrubber using 10% sodium hy-
droxide. This is fine unless something springs a leak. The
company distributed a book on phosgene in 1998.7 There
has been some concern about the development of phosgene
in chloroform that has been stored a long time.8 The best
solution is to use solvents other than chloroform (a car-
cinogen). The largest industrial use of phosgene is in the
preparation of isocyanates, most of which are used for
polyurethanes. Some isocyanates are also used to make
agricultural chemicals. The second major use is in the
preparation of polycarbonates.
In the laboratory bis(trichloromethyl)carbonate
(triphosgene; 2.2) (mp 79–83°C) can be used in place of
phosgene for greater safety and convenience.1,9 The
28
2.1
Aldrich Chemical Co. catalog describes it as a moisture-
sensitive lachrymator that should be handled with gloves in
a hood.
Cl3COCOOCCl3
(2.2)
triphosgene
Many investigators are studying ways to make iso-
cyanates and polycarbonates without the use of phosgene.
Their efforts will be reviewed in the following sections.
II. PREPARATION OF ISOCYANATES
The usual method of preparation can be illustrated by that
of toluenediisocyanate (2.1) a reagent that is then reacted
with diols to form polyurethanes10 (see also reviews11).
2.2
Chapter 2
Most of the weight of the phosgene is lost as hydrogen
chloride, which is probably neutralized to form salts that
are discarded. Other commonly used diisocyanates are also
made by reacting the diamines with phosgene (2.2).
The diisocyanates are reacted with diols to produce
polyurethanes that end up in consumer products, such as
seat cushions, mattresses, insulation, car bumpers, swim
suits, floor coatings, paints, and adhesives.12 The aromatic
diisocyanates are cheaper, but yield less light-stable poly-
mers than the aliphatic ones.
A. Other Ways to Make Isocyanates from
Amines
The tragedy at Bhopal13 involved methyl isocyanate. It is
reacted with 1-naphthol to make a carbamate insecticide
(2.3).
Doing Without Phosgene
2.3
The du Pont Co. has developed a method (2.3) to pro-
duce methyl isocyanate on demand so that it need not be
stored. The company no longer needs to ship tank cars of it
from West Virginia to the Gulf Coast, and the new process
is cheaper.14 (As mentioned in Chap. 1, integrated pest
management involving Bacillus thuringiensis could re-
place this insecticide.)
O2
CH3NH2  CO → CH3NHCHO → CH3NCO
240°C
84–89% yield
at 85–97% conversion
(2.3)
The reaction can be run in a minireactor with a silver cata-
lyst in etched channels.15 However, neighbors to the Rhone–
Poulenc plant in Institute, West Virginia are still concerned
about the 250,000 lb of methyl isocyanate stored there.16
A number of workers have treated both aliphatic and
aromatic amines with dialkyl carbonates to form urethanes
that can be pyrolyzed to isocyanates. Fu and Ono used a
lead catalyst with 95% selectivity (2.4).17 (The percentage
selectivity refers only to the amount of material reacted be-
cause the percentage conversion may not be 100%. In
many cases selectivity to the desired product drops as the
conversion nears 100%.)
Angeles et al. obtained 70–95% yields using a sodium
hydride catalyst.18 Aresta et al. made the urethanes with al-
most complete selectivity using phosphorus acids as cata-
lysts (2.4).19 This may involve an intermediate
2.4
29
(C6H5)2P(O)OCOOR. The phosphorus acid can be recov-
ered and does not contaminate the product. This is an im-
provement over their earlier work, which used an alkyl
halide, in that no by-product salts are formed.
base
RNH2  CO2  RX → RNHCOOR  baseHX
(2.4)
Tsujimoto et al. obtained a 98% yield of a bisurethane
(2.5).20
Then yields of isocyanates prepared by such routes can
be good. Romano made 1,6-diisocyanatohexane from hex-
amethylenediamine in an overall yield of 77% using a
sodium methoxide catalyst to form the intermediate
bisurethane.21 (Enichem is putting up a pilot plant to study
the commercialization of such processes.22) Ookawa et al.
ran a similar conversion to produce the diisocyanate in
92.5% yield with 1.2% monoisocyanate, which could be
recycled to the process (2.6).23
Lachowicz et al. also described a similar pyrolysis with
tin salts at only 140–145°C, but did not give the yield.24
(C4H9) 2 Sn (OC OC11H23)2
CH3COOCH2CH2NHCOOC4H9   →
CH3COOCH2CH2NCO
2.5
Much milder conditions were used by Valli and Alper (see
reaction 2.7), but pose a problem of recycling of reagents.25
Boron trichloride was also used, instead of th catecholbo-
rane, to prepare toluene-2,4-diisocyanate in 92% yield.26
30 Chapter 2

2.5

2.6

2.7
Doing Without Phosgene
2.8
Knolker et al. prepared aromatic isocyanates in 41–99%
yield without isolation of a carbamate (2.8).27 With only
10% 4-dimethyl-aminopyridine, the yield dropped to 97%
and with 1% to 92%. Further work is needed to get other
amines to give such yields, to figure out how to recycle the
the by-products from the reagents, and to eliminate the
need for a solvent.
These reactions require a carbonate that is usually made
from phosgene (2.6).28
2 CH3OH  COCl2
 2 NaOH → CH3OCOOCH3  2 NaCl  2 H2O
(2.6)
Workers at Enichem have developed a commercial process
for producing dimethyl carbonate by the oxidative car-
bonylation of methanol using cobalt or copper catalysts
(2.7).29
2 CH3OH  CO
catalyst
 0.5 O2 → CH3OCOOCH3  H2O (2.7)
A selectivity of 96% was obtained when the reaction was
carried out in the gas phase at 130°C with a palladium(II)
chloride–copper(II) acetate–magnesium(II) chloride cata-
lyst.30 The reaction has also been run in a eutectic mixture
of copper(I) chloride–potassium chloride at 150°C, with
94–96% selectivity to dimethyl carbonate and 2–5% selec-
tivty to methyl ether (2.8).31 After the product distils out,
the molten salt can be used for the next run.
2.9
31
catalyst
2 CH3OH  CO2 → CH3OCOOCH3  H2O
(2.8)
Diphenyl carbonate can be made from dimethyl carbon-
ate by exchange with phenol (2.9).32 It can also be made di-
rectly from phenol (2.10), but the yields are not as high.33
A combination of palladium and manganese catalysts is
used. The water formed is sparged out with excess reaction
gas to shift the reaction to the desired product. Diphenyl
carbonate is preferred over dimethyl carbonate for produc-
tion of polycarbonates.
Routes that use relatively harmless carbon dioxide
(2.9) instead of the toxic carbon monoxide are also known,
but require further work to improve the yields before they
can be used commercially.34
catalyst
2 CH3OH  CO2 → CH3OCOOCH3  H2O (2.9)
Better catalysts than the current titanium ones are needed.
(It may be possible to find some by screening catalysts
from combinatorial syntheses in supercritical carbon diox-
ide with molecular sieves present to take up the water.
(Such techniques are described in Chaps. 5 and 8.) The sec-
ond route (2.11) uses urea. The ammonia can be recycled
(2.10) to the process to make more urea.
NH3  CO2 → NH2COONH 
4 → NH2CONH2
(2.10)
The cyanuric acid needs to be minimized or pyrolyzed to
isocyanic acid for reaction with ammonia to form urea. It
might also be fed into a urea to melamine process.
32 Chapter 2

2.10

Melamine (2,4,6-triamino-1,3,5-triazine) is used with
formaldehyde to produce resins for use in counter tops,
dishes, and such. A third route reacts carbon dioxide with
orthoesters or ketals using an iodide catalyst.35 The by-
product ketone can be reconverted to the ketal (2.11) and
used in the next run, so that there is no waste. The selectiv-
ity was 86% at 94% conversion using a cesium iodide cat-
alyst.
I
CO2  RC(OCH3)3→ CH3OCOOCH3  RCOOCH3
(2.11)
The dialkyl carbonates can also be used in benign alky-
lations (2.12), instead of toxic dialkyl sulfates and
iodoalkanes, with improved selectivity.36
methylaniline at 99.6% conversion. When zeolite NaX was
used, the selectivity to N,N-dimethylaniline was 95.6% at
100% conversion. (For more on the size and shape selec-
tivity of zeolite catalysts, see Chap. 6.) Benzene has been
alkylated to a 34.7:1 toluene/xylene mixture over a zirco-
nium–tungsten oxide catalyst at 100–200°C with 99.3%
conversion of the dimethyl carbonate.38 Methanol and
methyl ether also formed. Monoalkylation of arylacetoni-
triles can also be done with trimethylorthoformate in 70%
yield.39
Several variants on the dialkyl carbonate route to carba-
mates have been reported (2.13). Valli and Alper may have
made the carbonate in situ.40
RNH2  CO  0.5 O2 CH3OH
Pd on montmorillonite clay
(2.13)
  → RNHCOOCH
79–100%  H2O
3

ArOCH2X  CH3OCOOCH3 bip yridyl 210°C /6–12h

K2CO3
 → X
180– 200 ArOCHCH3
 CO2 (2.12) The process works for both aliphatic and aromatic amines.
Harstock et al. used anodic oxidation instead of oxygen
 CH3OH X  CN, COOCH3 (2.14).41

Excess dialkyl carbonate can be the solvent. No by-product ArNH2  CO  Pd(OCOCH3)2

(2.14)
salts are formed. The by-product alcohol and carbon diox-
ide could be recycled. Arylacetonitriles, phenols, aromatic Cu(OCOCH3)2 CH3OH → ArNHCOOCH3
amines, trialkylamines, acetylenes, silica, and titania can
also be alkylated with dialkyl carbonates. A number of processes proceed through intermediate
Alkylation of catechol with dimethyl carbonate in the ureas (2.15).42
presence of LiOH/Al2O3 at 553 K gave the monoether with
84% selectivity at 100% conversion. Some 3-methylcate- C4H9NH2  CO  0.5 O2
chol also formed in the process.37 When the reaction of ani-
→ C4H9 NHCONHC4H9 (2.15)
line with dimethyl carbonate is carried out in the gas phase
CH3OH
with zeolite KY, the reaction was 93.5% selective for N- → C4H9NHCOOCH3  C4H9NH2

2.11
Doing Without Phosgene 33

2.12

With a palladium on charcoal catalyst, the selectivity to
carbamate is 97% (2.16).
C6H5NH2  CO  0.5 O2
MnBr2
→ C6H5NHCONHC6H5
↓
(2.16)
CO, 0.5 O2, CH3CH2OH
C6H5NHCOOCH2CH3
This is done all in one pot at up to 96.5% conversion of ani-
line with 94% selectivity. The use of a [Ru(CO)3I3]
(C4H9)4N catalyst gave the urea with 99% selectivity at
59% conversion.43
Another method makes the urea through the intermediate
acetoacetanilide (2.12):44 The catalyst was reused five times
with no loss in activity. The by-product acetone might be py-
rolyzed to ketene which would dimerize to diketene that
would react with more amine to form acetacetanilide. In an-
other variant from Asahi Chemical, ethyl N-phenylurethane
is reacted with formaldehyde (a carcinogen) to a bisurethane
(2.13) for thermal conversion to the diisocyanate.45
These processes that substitute carbon monoxide, oxy-
gen, and an alcohol for phosgene appear to be on the verge
of commercial viability. There may be questions of catalyst
life and recyclability that are not mentioned in the papers
and patents. Some reaction times need to be shortened
through the use of improved catalysts. Aresta et. al do say
that their palladium–copper catalyst system can be recy-
cled.46 The use of supported catalysts that could be recov-
ered by filtration could simplify workups and recycling.
(Supported catalysts are described in Chap. 5.)
McGhee and co-workers at Monsanto have studied the
preparation of isocyanates using nontoxic carbon dioxide
(instead of the poisonous carbon monoxide) with the amine
(2.17).47
RNH2  CO2  base → RNHCOObaseH
(2.17)
dehydrating agent
  → RNCO 94–98%

2.13
34
2.14
The preferred bases include triethylamine, amidines, and
guanidines. Dehydration of the carbamate has been done
with phosphorus trichloride, phosphorus oxytrichloride,
phosphorus pentoxide, acetic anhydride, benzenesulfonic
acid anhydride, o-sulfobenzoic anhydride (2.14), or other
similar compounds.
The phosphorus reagents led to a large amount of waste
salts. Acetic anhydride gave some competing formation of
amide. Although acetic acid can be reconverted to the an-
hydride thermally, benzenesulfonic acid cannot be, so that
recycling becomes a problem. (Benzenesulfonic acid anhy-
dride gave quantitative yields of isocyanates.) By-product
o-sulfobenzoic acid can be reconverted to the anhydride
thermally. Work is continuing to find the best no-waste
system that gives high yields.
Perhaps p-toluenesulfonic acid anhydride can be used.
The by-product toluenesulfonic acid is known to be con-
verted to the anhydride with phosphorus pentoxide in 88%
crude yield.48 The by-product phosphoric acid can be con-
verted back to the oxide or at least to polyphosphoric acid,
which should also work as the dehydrating agent. Use of
phosphorus pentoxide without the p-toluenesulfonic acid
anhydride may not give high enough yields. Perhaps a
scheme for regeneration of benzenesulfonic anhydride us-
ing phthalic anhydride or a copolymer of maleic anhydride
can be devised where the benzenesulfonic acid anhydride
distils out under reduced pressure as formed on heating.
The resulting carboxylic acid could be reconverted to the
anhydride on simple heating.
2.15
Chapter 2
The process can also be run to produce urethanes
(2.15).30 The urethane could be pyrolyzed to the iso-
cyanate. Recovery of the base would require treatment
with, perhaps, sodium hydroxide, which would give
sodium chloride as waste. Thus, the cost of the NaOH and
Cl is wasted. This group has also used guanidines (2.18) to
prepare mixed dialkyl carbonates.
ROH  CO2  guanidine  RCl
CH3CN (2.18)
→ ROCOOR  guanidine.HCl
Cooper and Falcone have used a similar system (2.16) to
make diarylureas in lower yields.49 When acetic anhydride
was used instead of the trimethylamine–sulfur trioxide
complex, the yield dropped from 59 to 57%.
B. Isocyanates from Nitro Compounds
Aromatic nitro compounds can be converted to carba-
mates by treatment with carbon monoxide and an alcohol,
usually methanol, in the presence of palladium, rhodium,
or ruthenium catalysts (2.19).50 Wehman et al. have re-
ported the best yields, which can be close to quantita-
tive.51
C6H5NO2  3 CO
Pd(II) catalyst
CH
 3OH
→ C6H5NHCOOCH3 (2.19)
 C6H5NHCONHC6H5  2 CO2
For dinitro compounds, using Pd(o-phenanthroline)2
(OSO2CF3)2 plus 4-chlorobenzoic acid, both mono- and di-
carbamates are formed. With increasing time all of the
monocarbamate can be converted to the dicarbamate. It is
possible that the by-product N,N-diphenylurea can be recy-
cled to the next reaction and be converted in situ to more
carbamate.
Such reactions may proceed by carbonylation of an in-
termediate palladium amide. Giannoccaro et al. have car-
ried out the stoichiometric reaction of amines with palla-
Doing Without Phosgene 35

2.16

dium and nickel compounds and carbon monoxide to pre- This approach, as exemplified by the work of Wehman
pare isocyanates (2.20).52 et al., appears ripe for commercialization. Drawbacks of
the reaction are the need for three equivalents of carbon
[(C6H5)3P]2PdClNHR  CO →
monoxide and relatively large amounts of noble metal cat-
CuCl2
[(C6H5)3P]2PdClCONHR → (2.20) alysts. The use of relatively high levels of catalyst is not a
problem if the catalyst can be used over a long time period
[RNHCOCl] → RNCO  HCl
and has good activity, as in a column in a continuous pro-
The reaction of the nitro compound has also been car- cess. A variant (2.22) using a 1:1 molar ratio of nitroben-
ried out with a heteropolyacid as part of the catalyst zene to aniline eliminates the need for the noble metal cat-
(2.21).53 alyst.57 The catalyst is a mixture of sulfur, sodium
methoxide, and ammonium metavanadate.
C6H5NO2  CO  CH3OH
C6H5NO2  3 CO  C6H5NH2
PdCl2
NH4VO3
H5PV2 Mo10 O 40
  → C6H5NHCOOCH3 (2.21) → C6H5NHCONHC6H5
CH3OCH2CH2OCH3 98% conversion (2.22)
CH3OH
170°C/3h 96% selectivity → C6H5NHCOOCH3
96% at 100%
Under less favorable conditions with palladium catalysts,
conversion
other workers have found aniline, azobenzene, and azoxy-
benzene as by-products.54 Further work on these various processes may be needed
The yields reported with ruthenium catalysts are lower to optimize catalyst life, separation, and recycle, as well as
than with palladium catalysts. Mukherjee et al. reacted ni- reaction rates. The preferred solvent, if any is required,
trobenzene with carbon monoxide and methanol with a would be ethanol instead of methanol, for the former is less
sodium methoxide plus ruthenium catalyst to give 80% car- toxic and can be produced readily from renewable sources
bamate and 18% aniline.55 Based on the mechanism sug- by fermentatation (see Chap. 9).
gested by Giannoccaro et al., it should be possible to recy-
C. Isocyanates from Isocyanic Acid
cle the aniline to the next run. Gargulak et al. used a
Ru((C6H5)2PCH2CH2P(C6H5)2)(CO)3 catalyst with ni-
Tertiary aliphatic isocyanates can be made by addition of
trobenzene to prepare the carbamate.56 They felt that their
isocyanic acid (a toxic material) to olefins (2.17). Cytec
catalyst is an improvement over the short lifetimes of ear-
(formerly American Cyanamid) makes a diisocyanate this
lier ones.
way.58 The reaction can be controlled to produce the
monoadduct which can be used as a monomer. Tertiary iso-
cyanates of this type react at lower rates than primary ones
in addition reactions. The isocyanic acid can be produced
by the pyrolysis of cyanuric acid which, in turn, can be pre-
pared from the urea (reaction 2.18).
The method is also applicable to -pinene (from pine
trees), which is cheaper than petroleum-based diiso-
propenylbenzenes.59 The reaction (2.19) can be carried out
to produce either the mono- or diadduct. Alternate routes to
the diadduct might be based on 1,8-diamino-p-menthane
(from Rohm & Haas) using the methods in Sec. II.A, as
long as no high temperature pyrolyses were used to recover
2.17 the isocyanate from a carbamate.
36
2.18
Isocyanates can also be made by reaction of salts of iso-
cyanic acid with alkyl halides (2.23).60 A disadvantage is
that this produces by-product salt.
C2H5Br  KNCO → C2H5NCO  KBr (2.23)
This method has been applied to a monomer synthesis
(2.20).61 The quaternary ammonium salt is used as a phase
transfer catalyst. The potassium iodide converts the starting
chloride to a more reactive iodide in situ. The alcohol traps
the intermediate isocyanate before it can react with the small
amount of water that has to be present. If no methanol is pre-
sent, the corresponding urea is formed in up to 87% yield. If
only 0.3 equivalent of water is used, the product is the iso-
cyanurate, the cyclic trimer of the isocyanate. Where n  1,
the isocyanatoethyl methacrylate is a useful monomer now
made with phosgene (2.21).62 Dow has patented a route
from ethanolamine plus a dialkyl carbonate, followed trans-
esterification to a methacrylate carbamate, which is py-
rolyzed to the isocyanate (2.22) in 50% yield.63
D. Isocyanates by Addition of Urethanes to
Double Bonds
Ethyl urethane (a carcinogen) can be added to activated
double bonds in the presence of palladium catalysts to give
a mixture of cis and trans adducts (2.23).64
If such addition reactions can be carried out cleanly in
high yields, di- and polyisocyanates might be made from
ethylenediacrylate, N,N-methylenebis(acrylamide), an un-
saturated polyester made from maleic anhydride. However,
it would be desirable to find a noncarcinogenic analogue of
the ethyl urethane, preferably one for which the adduct
2.19
Chapter 2
would unblock at a lower temperature. It may also be nec-
essary to hydrogenate the double bonds before unblocking.
E. Isocyanates by Rearrangements
Isocyanates can also be made by a number of rearrange-
ments of carboxylic acid derivatives that proceed via ni-
trenes (2.24).
Of these, the most practical commercially would be the
one based on amides. Terephthalamide (easily made from
inexpensive dimethyl terephthalate) and its cyclohexyl
analogue have been converted to isocyanates via N-chloro
compounds (2.25).65
A more direct route has been used to prepare carbamates
from aliphatic carboxylic acid amides (2.24).66
RCONH2  NaOCl  NaOH  CH3OH
with or with out
 → RNHCOOOCH3 R  C6–C11
hydrotrope and surf actant
(2.24)
(A hydrotrope is a compound that helps other compounds
normally not very soluble in water to dissolve in water.)
The one used was (2.26). Pyrolysis of the carbamate (ob-
tained in 90–96% yield) would lead to the isocyanate. This
type of reaction can also be carried out in 95% yield using
N-bromosuccinimide and sodium methoxide in methanol
or with bromine and sodium hydroxide.67 This suggests the
possibility of generating the bromine or iodine during the
reaction by electrolysis of sodium bromide or sodium io-
dide so that no waste salts result. The starting amides can
be made by heating the ammonium salts of the acids. This
Doing Without Phosgene 37

2.20

2.21

2.22

2.23

2.24
38
2.25
method does have the disadvantage of producing by-prod-
uct salts.
It is conceivable that the Lossen rearrangement
(Eq 2.25) might be practical commercially.
NH2OH
RCOOCH3 → RCONHOH
(2.25)
(CH3CO)2O
→ RNCO  CH3COOH
Hydroxylamine can be prepared from ammonia and hydro-
gen peroxide using a titanium silicalite catalyst in 83%
yield.68 The by-product acetic acid could be recycled to
acetic anhydride by pyrolyzing part of it to ketene.
F. Reducing the Toxicity of Isocyanates
Isocyanates can be dangerous, as shown by the tragedy with
methyl isocyanate at Bhopal. Several workers at W. L. Gore
Associates (Newark, Delaware) suffered disabilities while
using isocyanates, probably toluenediisocyanate, outside of
a hood. Isocyanates are the most common class of chemi-
cals causing occupational asthma.69 The problems are
greater in small businesses, such as decorating or small car
spraying, for which safety precautions are less likely to be
used. To enable the isocyanates to be used outside of a hood,
it is necessary to reduce this toxicity. This can be done by
increasing their molecular weight, which decreases the va-
por pressure, or by generating them in situ. A common way
is to react one of two isocyanate groups selectively (2.27).
An isocyanate may form a dimer or trimer.70
The trimer is a useful stiffening structure in some
polyurethanes. Phosphine oxides or phosphates can convert
an isocyanate to a carbodiimide (2.28). This is used com-
2.26
Chapter 2
mercially to convert some 4,4-diphenyldiisocyanate to the
carbodiimide so that the resulting product is a liquid that
may be easier to handle than the starting solid. If both iso-
cyanate groups react, the result is a polycarbodiimide that is
useful for cross-linking coatings.71 Polycarbodiimides can
be blocked with diethylamine so that they are inert until the
amine is released as a powder coating is cured by heating.72
[Powder coatings (which contain no solvents) are discussed
in Chap. 8.] Another common method is to react an excess
of diisocyanate with a diol, (e.g., a polymeric diol), as in the
following (2.29), which is used to repair deteriorating stone
by curing with moisture.73
In this compound, one isocyanate group is more reactive
than the other. Another approach is to prepare a diiso-
cyanate from an amine-terminated polymer, such as amine-
terminated poly(ethylene oxide).
Various HA-type reagents can add to the isocyanate
group (2.26).
RNCO  HA → RNHCOA (2.26)
For polyurethanes HA is an alcohol; for polyureas it is an
amine. This type of reaction can be used to block an iso-
cyanate and make it unreactive to water, until unblocking is
done thermally with loss of a volatile blocking agent. For ex-
ample, a polypropyleneglycol urethane prepolymer with iso-
cyanate groups blocked with methylethylketoxime can be
used with 2,2-bis(hydroxylmethyl)propionic acid and
tetraethylenepentamine in a one-package, cross-linkable, wa-
terborne coating. Deblocking occurs at 110–140°C after the
water has evaporated.75 It is necessary to recover the
methylethylketoxime from the exhaust air so that it can be re-
cycled, instead of being let out to pollute the surrounding air.
2.27
Doing Without Phosgene
2.28
Similarly, an aqueous treatment for wool uses an isocyanate
blocked with a bisulfite. In this case, the by-product bisulfite
salt can be removed, and possibly recycled, by washing the
fabric with water at the end. The dissociation temperature de-
creases in the following order: alcohol  lactam  phenol 
ketoxime  active methylene compound. -Caprolactam is a
typical lactam, ethyl acetoacetate a typical active methylene
compound. This thermal reversibility has been used to pre-
pare a polyurethane from 1,4-butanediol, 4,4-diphenyldiiso-
cyanate, and 4,4-isopropylidenediphenol (bisphenol A)
(2.30) that can be recycled just by remolding.76
Another way to make an isocyanate that is part of a
polymer is to polymerize an isocyanate monomer alone or
with comonomers. Typical isocyanate monomers are
shown in structure 2.31.77
Use of these comonomers in minor amounts can lead to
cross-linkable polymers. For example, Yukawa et al.
copolymerized isopropenylcumylisocyanate with butyl
acrylate and then performed a series of blocking and fur-
ther polymerization steps to prepare a waterborne coating
for cars. Methacryloylisocyanate was reacted with
bisphenol A to yield a new monomer.78 It is possible that
some of these isocyanate copolymers might be used to re-
place some resins now made with the carcinogen,
formaldehyde (e.g., in crease-proofing cotton textiles). It
may also be possible to use a blocked isocyanate
monomer to make copolymers in which the isocyanate
can be unblocked thermally for curing. A final way to put
an isocyanate group into a polymer is to run a Hofmann
2.29
39
reaction on a copolymer of acrylamide. The isocyanate
groups formed could be trapped with a blocking agent or
used directly.
III. POLYCARBONATES
The traditional preparation of polycarbonates uses phos-
gene (2.32).79 This can be carried out in solution with
pyridine as a base or in an interfacial system with sodium
hydroxide as a base and methylene chloride as a solvent.
This method is being displaced by an ester exchange
method (2.33) with diphenyl carbonate which requires no
solvent and produces no salts. It does require high tem-
peratures and a good vacuum or nitrogen flow to extract
the last of the phenol (bp 182°C) out. Asahi Chemical
uses a solid-state polymerization on a powdered prepoly-
mer to extract the phenol more easily to give molecular
weights of 60,000 or more.80 Numerous patents describe
a variety of basic catalysts and conditions for this reaction
with diphenyl carbonate.81 Bis(2,2,2-trichloroethyl) car-
bonate has also been used to make this polymer at
200°C.82 Dimethyl carbonate has been used with 1,4-cy-
clohexanedimethanol to prepare a biodegradable, biocom-
patible polymer.83
IV. SUMMARY AND CONCLUSIONS
Polycarbonates and polyurethanes are so useful that they
are here to stay. Elimination of phosgene in the preparation
40 Chapter 2

2.30

2.31

2.32

2.33
Doing Without Phosgene
2.34
of the former is now commercial at General Electric. With
recent improvements in the syntheses of isocyanates with-
out phosgene, the industry is on the verge of a commercial
process eliminating it here also. duPont has developed a
way to make methyl isocyanate on demand so that it does
not need to be stored or shipped. Going one step farther, a
combination of integrated pest management, pyrethrin in-
secticides and neem antifeedants might eliminate the need
to make carbamate insecticides altogether. Thus, most of
the steps in the hierarchy of approaches outlined in the in-
troduction to this chapter are being tried.
The challenge now is to make other isocyanates in
closed systems on demand so that they do not need to be
stored or shipped before being converted to less volatile
products or to blocked reagents. Even better, use systems
that trap them in harmless forms in situ. Some of the
reagents used to make the raw materials for isocyanates are
dangerous in their own right (e.g., the reaction of two car-
cinogens to produce 4,4-diaminodiphenylamine (2.34).
Some rethinking may be needed to use less harmful mate-
rials to end up with similar properties in the final
polyurethane. Polymers made from the foregoing reagent
need stiffness. Because amines can be made from alcohols
and ammonia with nickel or ruthenium catalysts, the fol-
lowing stiffeners (2.35) are possible. Eastman Chemical
uses this cis–trans mixture of diols to make a polyester.
Another stiffening possibility is (2.36). The alternative is to
use the foregoing cyclic diols as stiffeners with more flex-
ible aliphatic diisocyanates. Such changes will depend on
relative costs, extent of changes required in the plants, the
perceived danger of the carcinogens, and the demand for
light-stable polyurethanes.
2.35
41
There is the question of just how toxic one intermediate is
relative to another. In the alternative methods that avoid
phosgene, carbon dioxide is less toxic than carbon monox-
ide; ethanol is less toxic than methanol, suggesting the use of
diethyl carbonate instead of dimethyl carbonate; the
aliphatic amine intermediates are less toxic than the aromatic
amines and the nitro compounds from which the latter are
made; routes to amines from diols are less dangerous than
those going through nitriles; higher molecular weight ana-
logues are less toxic (by inhalation) than those of lower
molecular weight; routes via carboxylic acids may be less
dangerous than those via nitro compounds and a solid might
be less likely to give problems than a liquid that might pen-
etrate the skin. If the material is not a problem in ordinary us-
age, or if the alternative costs a lot more to make, it probably
will not be displaced. If it is a minor problem, then contain-
ment and good occupational hygiene may be the answer.
Some processes that claim replacements for phosgene
still use dangerous material. Manada and Murakami have
made methyl chloroformate without phosgene as follows
(2.27):84
4 NO  O2  4 CH3OH → 4 CH3ONO  2 H2O
60°C. ↓ NOCl, CO
ClCOOCH3  2 NO
(2.27)
Items for further study include the following:
1. Use of an HA reagent that will make it easier to re-
cover the isocyanate than is possible with RNHCOOCH3.
42
2.36
2.37
Could diphenyl carbonate replace dimethyl carbonate, at
least for isocyanates that boil appreciably higher than phe-
nol? Could methylethylketoxime or ethyl acetoacetate fit
into some of the syntheses?
2. Will the duPont method for methyl isocyanate work
for higher aliphatic amines and aromatic amines? The
patent claims amines up to ten carbon atoms but gives no
examples. Could this method be adapted for use with
copolymers of N-vinylformamide?
3. Ureas can be prepared from amines and carbon
dioxide.85 They can also be prepared by heating amines
with urea at 160°C.86 Treatment with excess alcohol (or
other hydroxyl compound) would give a carbamate (or ana-
logue) for pyrolysis to an isocyanate (2.36).
The methanolysis of N,N-dibutylurea to give the carba-
mate is known.87 This would overcome some of the prob-
lems of the Monsanto synthesis.
4. Phenol can be converted to aniline by treatment
with ammonia at high temperatures. Can a nickel, ruthe-
nium, or other metal catalyst be found to do this for aro-
matic diols, such as 4,4-isopropylidenediphenol or 4,4-
sulfonyldiphenol?
The product shown in structure 2.37 is a known com-
pound that can be made from aniline hydrochloride and
acetone in 74% yield.88 It has also been made by reduction
of the corresponding dinitro compound.89 Another possi-
bility is to reduce the bisphenol to the corresponding dial-
chohol, which can then be treated with ammonia to produce
a diamine.
5. Methyl N-phenylcarbamate has been reacted with
formaldehyde to give a biscarbamate that was pyrolyzed
to 4,4-diisocyanatodiphenylmethane. Can a catalyst be
Chapter 2
found so that acetone can be substituted for formalde-
hyde?
6. Is there a way of oxidizing an amide to a hydrox-
amic acid that can then undergo a Lossen rearrangement in
situ? This might be possible with hydrogen peroxide and ti-
tanium silicalite (or a related system) or with a dioxirane.
REFERENCES
1. T.A. Ryan, C. Ryan, E.A. Seddon, and K. Seddon, Phos-
gene and Related Carbonyl Halides, Elsevier, Amsterdam,
1996.
2. W. Schneider and W. Diller, Ullmann’s Encyclopedia of In-
dustrial Chemistry, 5th ed., 1991, A19, 411.
3. Chem. Eng. News, Jan 29, 1996, 17.
4. Chem. Eng. News, July 15, 1996, 13.
5. Chem. Eng. News, Dec. 11, 1995, 20.
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Doing Without Phosgene 45

NOTE ADDED IN PROOF EXERCISES

Dimethyl carbonate has also been prepared from urea and 1. Methyl isocyanate was involved in the tragedy at
methanol in triglyme using the technique of reactive distil- Bhopal. What would our society have to do to get
lation.90 The byproduct ammonia can be reacted with car- along without it altogether?
bon dioxide to make more urea. 2. Devise a copolymer containing blocked isocyanate
tryglyme
CH3OH  NH2CONH2 →[NH2COOCH3]  NH3 groups, such that on reaction with a difunctional
heat

↓
CH3OH
CH3OCOOCH3  NH3
98.2% selectivity at 98.3% conversion
RECOMMENDED READING
1. W. Schneider and W. Diller, Ullmann’s Encyclopedia of In-
dustrial Chemistry 5th ed., 1991; A19, 411-(on phosgene).
2. K. Weissermel and H.-J. Arpe, Industrial Organic Chem-
istry, 2nd ed., 1993, pp. 373–379-(on isocyanates).
3. R.H. Richter and R.D. Priester, Jr., Kirk–Othmer Encyclope-
dia of Chemical Technology 4th ed., 1995, 14, pp. 906–908,
918–924 (making isocyanates without phosgene).
4. K.J. Saunders, Organic Polymer Chemistry, 2nd ed., Chap-
man & Hall, London, 1988, pp 269–272 (preparation of poly-
carbonates).
5. J. Jarvis, R. Aguis, and L. Sawyer, Chem. Br., 1996, 32(6), 51
(chemicals and asthma).
reagent to cure it, no reblocking would occur, and
no volatile compound would come off.
3. Dimethyl carbonate can be used to alkylate phenols,
aromatic amines, acetylenes, and active methylene
compounds. What other alkylations might be car-
ried out with it that are now performed with
iodomethane or dimethyl sulfate?
4. Go through the various syntheses for isocyanates
and figure out how to recycle all the by-products to
the processes, wherever possible.
5. Other dangerous, but widely used, chemicals that
need to be replaced by less hazardous ones include
formaldehyde, benzene, acrylonitrile, hydrogen
cyanide, and hydrogen fluoride. Pick one and see
what would be involved in making the same end-
use products without it.
3
The Chlorine Controversy
I. THE PROBLEM
Greenpeace and other environmental organizations have
called for the phasing out of chlorine and the products made
using it.1 Other groups, including the Society of Toxicol-
ogy, American Medical Association (AMA), the American
Chemical Society (ACS),2 Michigan Environmental Sci-
ence Board,3 American Chemical Council (formerly Chem-
ical Manufacturers Association) Chemical Manufacturers
Association Chlorine Chemistry Council,4 American Indus-
trial Health Council,5 and United Kingdom (U. K.) Chemi-
cal Industries Association,6 have said that this is unneces-
sary. The last calls the request the result of chlorophobia. It
points out that there are about 1500 natural chlorine-con-
taining compounds, including epibatidine (3.1), a pain killer
200 times more powerful than morphine, which is used by
an Ecuadorian tree frog for defense. It is a highly poisonous
nerve toxin used by natives in their blowpipes. Gribble has
also called attention to about 2000 natural chlorine com-
pounds, including many from marine algae.7 (Marine algae
contain vanadium haloperoxidases that catalyze halogena-
tions.8) One group of fungi, basidomycetes, even produce
chloromethane as well as chlorinated aromatic compounds.9
Methyl bromide is emitted by Brassica plants (in the mus-
tard family).10 Bromophenols are part of the prized flavor of
shrimp.11 These natural halogen compounds include at least
3.1
47
two that are essential for human life, hydrochloric acid in
the stomach and thyroxine (3.2) in the thyroid gland.
(The status of the chlorine debate has been reviewed.12)
Our society uses a great many products containing chlo-
rine, as seen in Table 3.1, from Chemical Engineering
News.13 The chlorine industry in Europe used 10 million
metric tons of chlorine in 1992. Of this, 20% went into
polyvinyl chloride, 8% into intermediates, 6% into sol-
vents, 5% into other organic compounds, and 2% into inor-
ganic chemicals. About 36% ended up in hydrochloric
acid. The remaining 23% was disposed of as salt. This
amounted to 3.5 million tons of polyvinyl chloride;
761,000 tons of chlorinated paraffins and poly(chloro-
prene); 537,000 tons of solvents, such perchloroethylene
and methylene chloride; 561,000 tons of sodium hypochlo-
rite; and other inorganic chemicals. Products made with
chlorine, but not containing it, included 1.3 million tons of
intermediates for polyurethanes, 517,000 tons of other
resins and plastics, 447,000 tons of dyes and crop-protec-
tion chemicals, and 370,000 tons of inorganic compounds,
such as titanium dioxide.14 Chlorine is used in 98% of wa-
ter disinfection, in the production of 96% of agricultural
chemicals, and in making 85% of drugs.15
When phasing out the use of chlorine means major
changes for a large industry, why would environmental
groups ask for it? The answer is that halogen imparts sig-
3.2
48
Table 3.1 Chlorine Derivatives Are Used in a Hugh Array of Products
Vinyl chloride
Vinylidene chloride
Dichloroethyl ether
Methyl chloride
Ethyl chloride
Ethylene dichloride
Methylene chloride
Chloroform
Carbon tetrachloride
Allyl chloride
Benzoyl chloride
Chlorotoluenes,
chlorophenol
Benzotrichloride
p-Chlorobenzotrifluoride
Dichlorobenzene
Chloroprene
Dichlorophenyl sulfone
Phosgene
Propylene chlorohydrin
Source: Ref. 13 Reprinted with permission from B. Hileman, J.R. Long & E.M. Kirschner, Chem. Eng. News, Nov. 21, 1994, pp. 14–15. Copyright 1994
Chapter 3
Polyvinyl chloride Magnetic tape
Polyvinylidene chloride Pipes & fittings for sewer service Containers for food products, cosmetics,
Food packaging household chemicals
High-grade lubrication oils Garden hoses, lawn furniture
Clear plastic bottles Floor coverings, wallpaper
Vinyl ether
Anesthetics House siding, gutters, window frames
Paints, varnishes, lacquers
Pipes & fittings
Chlorosilanes Semiconductors Film & sheeting
Methyl cellulose Thickening agent for foods, nonfoods
Silicones Medical devices, surgical membranes
Encapsulation of electronic parts
Caulking, sealing compounds
Cosmetics, pharmaceuticals
Time-release pharmaceuticals
Ethyl cellulose
Inks
Ethylenediamine Paper chemicals
Additives for oil, detergents
Nonstick cookware
Pharmaceuticals, cosmetics
Paint removers, process solvents
Dry cleaning
Epichlorohydrin Epoxy resins Surface coatings on autos, appliances
Glycerine Household glue for metals, glass, ceramic
Plastics
Pharmaceuticals
Pharmaceuticals
Dyes
Crop protection chemicals
Cosmetics
Oil-resistant auto components
Carpet backing
Neoprene
Wire coating
Shoe soles
Computer components
Polysulfone Housings for power tools, appliances
Electronic parts
Pharmaceuticals
Crop protection chemicals Bullet-proof glass
Shoe parts
Chemical intermediates Appliance housings
Polycarbonates Compact discs Auto bumpers, fenders
Insulation
Propylene oxide Polyurethane Adhesives
Sealants, caulking agents
Propylene glycols Plastics
Coatings
Solvents
Foam cushions, mattresses
Food additives
Antifreeze
Flavoring extracts
Lotions
Pharmaceuticals Lubricants
Metal-working fluids
Polypropylene glycols
Rubber
Coatings Plastics
Cleaners
Propylene glycol ethers
Intermediates Adhesives
Brake fluids Coatings
Corrosion inhibitors
Isopropanolamines
Cosmetics
Crop protection chemicals
Plastics
Table 3.1 (Continued)

Sugar relining
Corn syrup
Food processing
Gelatin
Desulfurization of petroleum Brewing

Alkyl chlorides Electronic silicone

Hydraulic acid
Oil well acidizing Catalysts
Metallic chlorides Refractories
Water treatment Alloys Rubber accelerators
Plastics stabilizers
Hydrochlorides
Rocket propellants
Polymers, ion-exchange resins Pharmaceuticals
Hair care products
Methyl chloroacetate Crop protection chemicals
Chloroacetic acid Synthetic caffeine, vitamins
Pharmaceuticals
Thickeners, food additives

Liniments
Trichloroacetaldehyde
Pharmaceuticals
Tetrachlorophthalic Flame retardants
anhydride Cable insulation
Chlorinated olefins Highway stripe paint
and paraffins Flame retardants
Detergents

Sulfur dichloride Photographic chemicals, dyes

Sulfur monochloride Rubber antioxidants
Thionyl chloride Adhesive bandages
Sulfuryl chloride Pacemaker batteries

Gasoline additives
Phosphorus trichloride Intermediates
Phosphorus pentachloride Semiconductors
Phosphorus oxychloride Flame retardants
Crop protection chemicals
Photography, etching, engraving
Ferric chloride Water treatment
Printed circuits
Silverizing mirrors
Stannous chloride
Stabilizer in soaps
Soldering fluxes
Zinc chloride Deodorants
Dental cements
Other metal Catalysts
chlorides Swimming pool sanitizers
Chlorinated Bleaches
isocyanurates Detergents for automatic dishwashers
Scouring powders

Bleaching pulp, paper

Sodium Water purification
hypochlorite Pharmaceuticals
Swimming pool disinfectant

Algicide, bactericide Transformer fluid

Calcium hypochlorite Deodorant Circuit boards
Water purification Drain cleaners
1, 1, 1-Trichloroethane
Leather finishing
Perchloroethylene
Dyes
Methylene chloride
Refrigerants
Trichloroethylene
Semiconductors Solvents
Paint pigment, opacifiers Adhesives
Titanium dioxide
Catalysts Dry cleaning
Synthetic gemstones
50
nificant biological activity to compounds. In the right
place, this has been very useful. Unfortunately, they, and
active metabolites from them, have collected into unin-
tended places, such as groundwater, rivers, and air.16 Once
in the air the compounds can travel long distances and
come to earth again in rain, or just by cooling of the air.17
There, some of them have created serious problems with
nontarget organisms. Unfortunately, some environmental
monitoring has focused only on the starting compound, ex-
cluding active metabolites derived from it; thus, giving a
distorted picture.
II. TOXICITY OF CHLORINE COMPOUNDS
As mentioned in Chapter 1, persistent highly chlorinated
compounds, such as DDT and polychlorinated biphenyls
(PCBs), have caused egg shell thinning in birds, leading to
reproductive failure. Running the standard toxicity tests on
rodents did not pick this up. (The heterocyclic compound,
C10H6N2Br4Cl2, has been found in the eggs of birds of the
Pacific Ocean. It is probably of natural origin, because it is
not found in the Great Lakes of the United States.18) Al-
though useful in applications such as protection of houses
from termites with chlordane, persistence in the environ-
ment has frequently turned out to be undesirable. Analysis
of tree bark samples has shown persistent organochlorine
pollutants to have global distribution.19 The concentration
in seabirds of Midway Island in the northern Pacific Ocean
is almost as high as in birds of the Great Lakes between
Canada and the United States.20 Polybromobiphenyl flame
retardants have been found in the blubber of sperm
whales.21 The concentration of the insecticide Toxaphene,
a mixture made by chlorinating camphene, in fishes of
Lake Laberge in the southern Yukon of Canada is high,
presumably the result of atmospheric deposition and bio-
magnification.22 This material and many other highly chlo-
rinated compounds have been banned in the United States
for many years. However, Toxaphene is still used in Cen-
tral America and Eurasia. The Nordic countries and the
Netherlands have called for a global ban on such persistent
organic pollutants.23 They point out that such insecticides
appear to be cheap and easy to apply, but when their ad-
verse effects on nontarget species are taken into account,
they are as expensive, or more so, than the alternatives. (In-
ternational negotiations on the ban are now in progress.24)
DDT was banned in the United States in 1973, but its more
toxic metabolite DDE, formed by dehydrohalogenation, is
still being detected in well water in the midwestern United
States.25 (For alternatives to pesticides see Chap. 11.)
Polychlorobiphenyls are responsible for many fish advi-
sories (which advise fishermen not to eat too much fish
Chapter 3
caught in the body of water). Mohawk Indians near
Massena, New York, who have eaten relatively large
amounts of fish contaminated with polychlorinated
biphenyls have a “very high rate of hypothroidism.” Their
children have “striking” increases in diabetes and asthma.26
Polychlorinated biphenyls were used as heat-transfer fluids
in plants processing edible oils. Leakage of these into the
oil caused more than 50 deaths of persons who ate the oil
in Japan in 1968 and 1973.27 Biphenyl–diphenyl ether flu-
ids are much less toxic and their presence can be detected
by odor at 1 ppm or more. Dredging of sediments has been
used to remove polychlorinated biphenyls from a lake in
Sweden,28 the New Bedford, Massachusetts harbor,29 the
Housatonic River in Massachusetts,30 and has been sug-
gested for the Hudson River in New York.31
Henschler has reviewed the toxicity of organochlorine
compounds.32 Many are carcinogens (e.g., vinyl chloride,
which is associated with liver and biliary tract cancers and
angiosarcomas).33 One of the most toxic is 2,3,7,8-tetra-
chlorodibenzo-p-dioxin (3.3).
When their paddocks were sprayed with waste oil con-
taining 33 ppm of this dioxin in 1971 in Missouri, 65 horses
died within a few weeks.34 In 1953, a runaway reaction in
a vat of trichlorophenol at BASF’s Ludwigshafen, Ger-
many, plant caused workers to be contaminated with this
dioxin. In addition to the chlorance that this caused in some
workers, there was an 18% increase in medical problems in
the exposed group.35 This included thyroid disease, intesti-
nal and respiratory infections, and disorders of the periph-
eral nervous system, as well as appendicitis. A 1976 acci-
dent that released kilogram quantities of dioxin near
Seveso, Italy resulted in a shift in the sex ratio of babies
born in the area until 1984. There were 26 males and 48 fe-
males. Normally 106 males are born for every 100 fe-
males.36 According to the report of the U. S. Environmen-
tal Protection Agency (EPA) dioxins, even in minute
amounts, can cause disruption of regulatory hormones, re-
productive and immune system disorders, and abnormal fe-
tal development.37 The dioxins present in the “Agent Or-
ange” used in the Vietnam War may have caused birth
defects and deformities.38 Physicians for Social Responsi-
bility, Environmental Defense, and others say that further
regulation of dioxin sources is necessary, because effects
on the fetus can occur at extremely low levels, levels that
now occur in the tissues of some subpopulations.39
3.3
The Chlorine Controversy
Waste combustion accounts for 95% of dioxin emis-
sions in the United States, with 5100 g from hospital incin-
erators, 3000 g from municipal incinerators and 35 g from
hazardous waste incinerators.40 (New regulations are de-
signed to reduce the amount from medical incinerators.41
Some dioxins originate from forest fires and other natural
sources.42) The annual global output of polychlorodibenzo-
p-dioxins and related dibenzofurans is about 13,000 kg/y.
Paper mills in the United States release 110 g of dioxins
and related materials each year. When bleaching is done
with chlorine dioxide instead of chlorine, dioxins drop be-
low the detectable level. One of the problems in hospitals
may be the use of gloves of polyvinyl chloride to avoid the
dermatitis in some workers that is caused by the protein in
natural rubber gloves. Guayule rubber is a possible alterna-
tive, as it is hypoallergenic.43 BASF has offered a vana-
dium oxide-containing catalyst for the removal of dioxins
from municipal waste incinerators, which is now being
used in at least two commercial installations in Germany.44
A study by Queens College of the State University of New
York concluded that eliminating dioxin sources would not
cause economic loss.45 This would be done by a combina-
tion of replacing incineration by recycling and installing
autoclaves to sterilize infectious waste at hospitals.
Some chloroacnegens, such as 3.4, are so potent that
drug companies hesitate to work with them.46 The
widespread use of triclosan (3.5) as a bactericide in personal
care products needs to be reduced now that several strains
of bacteria resistant to it have been isolated.47 Soap and wa-
ter alone will suffice in many of these applications. The use
of dichlobenil (3.6) to kill roots penetrating underground
pipes might be eliminated by designing tighter pipe joints.48
3.4
3.5
51
3.6
III. ESTROGEN MIMICS
Colburn et al. recently proposed that several synthetic
chemicals, especially highly chlorinated ones such as poly-
chlorinated biphenyls and insecticides, can act as hormone
mimics in wild life.49 These include feminized young male
alligators, in a Florida lake where a pesticide spill occurred
in 1980, feminized male birds, and feminized fish.50 On the
other hand, feminization of fish in some rivers in the United
Kingdom is due to human estrogens that are not removed
by the wastewater treatment plants.51 It has been suggested
that estrogen mimics52 may account for the declining ratio
of male to female births in Canada, Denmark, The Nether-
lands, and the United States;53 some of the increased levels
of breast cancer54 in developed countries; the two- to four-
fold rise in testicular cancer in industrialized countries; and
a drop in the sperm counts in some cities and countries.55
An alternative explanation for the lower sperm counts is the
wearing of tight underwear, which keeps the testes too
warm to function well.56 A dose–response relation has
been found for dieldrin (a highly chlorinated insecticide)
and breast cancer.57 On the other hand, the phytoestrogens
of soy products may account for the low incidence of breast
and prostate cancer in Japan.58 At one time, diethylstilbe-
strol (DES; 3.7) was used to prevent miscarriages in preg-
nant women. It was banned in 1971 after it was linked to a
rare vaginal cancer in the daughters of these women.
Other classes of commonly used compounds are also
under suspicion as hormone mimics. These include
alkylphenols and their reaction products with ethylene ox-
ide, which are used as detergents, as well as phthalates,
which are used as plasticizers.59 These detergents might be
replaced with alkyl polyglycosides that can be made from
renewable sugars and fats (see Chap. 12). Di-n-butyl
3.7
52
phthalate disrupts development in male rats, causing miss-
ing or displaced testes.60 A Swedish study found a seven-
fold greater incidence of testicular cancer among those who
worked with polyvinyl chloride-containing phthalates.61
There is concern about the use of dinonyl phthalate plasti-
cizers in polyvinyl chloride toys used by children younger
than the age of 3.62 Bans are being considered in the Euro-
pean Union (EU). There is also concern about the amount
of di(2-ethylhexyl) phthalate that leaches from the
polyvinyl chloride bags during intravenous administration
of nutrients and drugs.63 Adequate substitutes are already
available. Vinyl chloride can be copolymerized with a plas-
ticizing comonomer such as vinyl stearate or vinyl 2-ethyl-
hexanoate. Grafting butyl acrylate to polyvinyl chloride
also works.64 The polyvinyl chloride can be replaced by
ethylene–styrene copolymers65 or polypropylene plas-
tomer made with metallocene catalysts.
When pregnant mice are fed very small doses of bisphe-
nol A, their male offspring have enlarged prostates as
adults.66 This has caused concern about the use of polycar-
bonates made from this material in reusable baby bottles,
water carboys, and such.67 This may be a problem only if
the polymer is abused by heating it too long in water that is
too hot. Styrene and its dimer and trimer may also be en-
docrine disruptors.68 Most of the estrogenic compounds
have potencies of 0.02–0.0001 that of estradiol or diethyl-
stilbestrol. Many explanations, including estrogen mimics,
have been advanced for the decline in amphibian popula-
tions and the increased incidence of deformities in frogs.69
None has yet been proved.
The chemical industry is suspicious of the claims and is
hesitant to make changes based on them.70 However, in-
creased testing71 will be done. The U. S. Environmental
Protection Agency has finalized its testing procedure. 72
The American Chemistry Council has voted to spend
850,000 dollars to study the problem.73 The European
Modulators Steering Group of the European Chemical In-
dustry Council has started a 7 million dollar testing pro-
gram.74 Much other research is also planned.75
IV. BLEACHING PAPER
The traditional bleaching of paper with chlorine leads to an
effluent containing 45–90 kg of organic waste per ton of
pulp, of which 4–5 kg is organically bound chlorine.76
These include various chlorinated furanones, cyclopen-
tenediones, and other materials.77 These are derived from
lignin, humic acids, and such. Typical compounds are
structures 3.8 and 3.9.
These are weakly mutagenic in the Ames test. The
amount of chlorine per ton drops to 46 g for recycled
paper.78
Chapter 3
3.8
3.9
Various other reagents are being tried to reduce these
chlorinated materials as well as the chlorinated dioxins.
These include chlorine dioxide, hydrogen peroxide, oxy-
gen, peracids, ozone, dioxiranes, and enzymes.79 Most mills
switched to chlorine dioxide in the past decade to reduce the
levels of chlorinated dioxins.80 This reduced the other chlo-
rinated compounds to 0.9–1.7 kg/ton.81 When ozone is used
in combination with chlorine dioxide, 1 kg of ozone can
save up to 4 kg of chlorine dioxide.82 To eliminate all the
chlorinated compounds in the mill effluent, it is necessary
to go to a nonchlorine bleaching agent.83 This is being done
in some mills in Europe.84 When this is done, the resin and
fatty acids in the effluent still exhibit harmful sublethal ef-
fects on the fish in the stream. To avoid this, some mills have
switched to closed systems with a total recycle of water.
More will do so as they work out the technical problems in-
volved (e.g., deposits that tend to build up).85
Pulp can be bleached with hydrogen peroxide.86 Sodium
perborate works just as well.87 Polyoxometalates can be
used with hydrogen peroxide or oxygen so that the capital
cost is only 1% of that of a comparable plant using ozone.88
(For other uses of polyoxometalates, see Chap. 6.) Transi-
tion metal ions in the wrong form can decompose the hy-
drogen peroxide. Sodium silicate is used to prevent this,
but scale deposits may build up. Dow Chemical is market-
ing a new complexing agent that avoids this problem.89 The
bleaching by hydrogen peroxide works better if a prebleach
with ozone or chlorine dioxide is used. It works even better
if ethylenediaminetetraacetic acid (EDTA) is added after
the pretreatment, but before the hydrogen peroxide.90
Collins and co-workers have studied the ways that the or-
ganic ligand in a metal catalyst can be oxidized, then they
have altered the structure to avoid these. The result is a cat-
alyst (3.10) that can be used with hydrogen peroxide to
bleach paper pulp, as well as dyes in wastewater.91
The Chlorine Controversy
3.10
Some dyes in dye effluent can also be decolorized with
hydrogen peroxide in the presence of ultraviolet (UV)
light.92 This facilitates reuse of the wastewater. Cheaper
hydrogen peroxide may become available if processes
preparing it directly from hydrogen and oxygen with a
palladium catalyst prove to be practical.93 A system for
generating hydrogen peroxide on site electrochemically is
also under development.94 These would increase the in-
centive to replace both chlorine and chlorine dioxide.
Peracids have also been used to bleach paper pulp,95 as
well as jute and cotton.96 (Cotton can also be bleached
with hydrogen peroxide, instead of the usual sodium
hypochlorite.97)
One plant in Sweden produces 315,000 ton/yr of pulp
that is bleached with ozone. The pulp is just as strong as the
standard pulp bleached with chlorine. Almost all (95%) of
the effluent waste is recycled.98 Ozone is also being used to
bleach Eucalyptus in Brazil.99 Dioxiranes work well in
bleaching pulp. They can be generated in situ from a ketone
and peroxymonosulfate ion (3.11).100
Xylanases are being used in a prebleaching step to re-
move some of the hemicellulose present.101 These reduce
the amount of chemical bleaching agent needed. They are
followed by chlorine dioxide, hydrogen peroxide,
dimethyldioxirane, or some other bleaching agent. The en-
zymes must be free of cellulases. Most work at 37°C, but a
few, derived from thermophilic organisms, are effective at
55°C and 65°C. One derived from Streptomyces thermovi-
olaceus is effective in a 3-h pretreatment at 65°C when fol-
lowed by hydrogen peroxide.
Organochlorine compounds are also found in the
wastewater when wool is treated with chlorine in the “Her-
cosett” process for shrink-proofing wool. Several shrink-
proofing processes that use no chlorine have been devised:
3.11
53
(1) hydrogen peroxide pretreatment, followed by chi-
tosan,102 (2) crosslinking with glycerol triglycidyl ether;103
(3) curing a mixture of a difunctional acrylate and an
epoxysilicone with ultraviolet light;104 and (4) 2-min pre-
treatment in a glow discharge followed by application of a
cationic acrylic copolymer.105
V. DISINFECTING WATER
Chlorine was first used to disinfect water106 in Jersey City,
New Jersey in 1908. It kills many microorganisms that can
be present in water, including those that cause cholera, ty-
phoid, dysentery, and hepatitis.107 It has saved a huge num-
ber of lives. Even so, there have been 116 disease outbreaks
in the United States since 1986 owing to contaminated tap
water.108 In the process of chlorinating water, small
amounts of chloroform,109 a carcinogen, are formed by
chlorination of natural organic matter in the water. Since
1979 the U. S. Environmental Protection Agency has lim-
ited the level to 100 ppb. A new level of 0.3 mg/L has been
proposed.110 However, a study in California found an in-
crease in the incidence of miscarriages when the level was
higher than 75 g / L.111 Disinfection with chloroamines
eliminates the chloroform, but sometimes forms some
highly toxic cyanogen chloride as a by-product.112 Poly-
meric N-haloamines have been used to coat surfaces of
glass and plastics.113 The use of sodium hypochlorite in
food sterilization in Japan led to 250 ppb chloroform in one
product. When phosphoric acid was used instead, almost
no chloroform was present.114 Chlorination of the cold wa-
ter around poultry being processed resulted in one of the
most potent mutagens known (3.12):
3.12
54
It could be deactivated by sodium bisulfite or L-cysteine.115
Substitution of chlorine dioxide for chlorine in the poultry
chiller water gave no mutagenicity. No chloroform is
formed when this reagent is used.116
Ozone can be used to sterilize water, but it has no
residual action once the water gets into the distribution
pipe.117 It could reduce the amount of chlorine or sodium
hypochlorite needed. It might also produce traces of
formaldehyde, a carcinogen, in the water. A combination
of ultraviolet light and titanium dioxide is also being stud-
ied as a means of disinfecting air and water.118 The sys-
tem works, but the quantum yields may be somewhat low
for an economical process.119 It is said to destroy those
cyanobacterial toxins that conventional treatment methods
do not remove.120 Pulsed ultraviolet light from a xenon
flash bulb is said to destroy pathogens, including Cryp-
tosporidium, which is not affected by chlorine, at a price
comparable with chlorination.121 (A 1993 outbreak of
Cryptosporidium infection in Milwaukee, Wisconsin,
sickened 400,000 persons and several died.) No chemicals
are required and no chloroform or other by-products form.
The system has also been supplemented with ultrasound
and electromagnetic fields in Phoenix, Arizona.122 A
combination of ultraviolet light and hydrogen peroxide is
also being used in plants today.123
Sterilization by purely physical means would eliminate
the questionable by-products. The classic method is to
boil the water, but this is probably too energy-intensive
for city water supplies. There have been proposals for
dual water supplies in homes, with a small line for drink-
ing water and a larger one for flushing the toilets and wa-
tering the lawn. While this would be very costly to retrofit
communities, it would allow more options in how munic-
ipal water is treated. Campers use biological filters to
clean-up water for drinking. With proper prefiltration to
remove larger particles, this might be feasible. The
throughput would have to be high and the membrane
would have to resist fouling or be easy to clean. Use of a
membrane with built-in polymeric quaternary ammonium
salts124 would be even better. Food is sometimes sterilized
by high pressure, with or without heat and ultrasound, a
process that is in commercial use in Japan today.125 Food
has also been sterilized with pulsed electric fields. High-
intensity ultrasound is often used to disrupt bacterial cells.
This should be feasible, although the energy costs would
need to be studied carefully. Low-cost disinfection of wa-
ter by passing it through titanium alloy plates charged
with direct current is being used in Brazil. It is said to cost
one-fifth as much as traditional technologies.126 It cer-
tainly should be studied for application elsewhere. High-
energy electron beams are being used to disinfect water in
a pilot facility in Miami, Florida.127 Gamma rays from a
60
Co source offer another alternative. This could be a re-
Chapter 3
stricted option, because handling the radioactive source
requires considerable care.
Treated wastewater from municipal sewage plants
requires a treatment with chlorine before discharge into
a river, at least in the warmer months of the year. Because
the residual chlorine can kill the flora and fauna of the
river, the treated wastewater is usually treated further with
sulfur dioxide or sodium bisulfite to remove the chlo-
rine.128 This seems like an ideal place to use alternative
methods of disinfection, because no residual activity is
needed or desired. Disinfection with ultraviolet light is now
a viable alternative.129
It is certainly possible to disinfect water without using
chlorine or compounds containing it. Further study is
needed on the need for residual activity in the distribution
system of cities, the possible toxicity of the products of al-
ternative reagents, and the relative costs of the various sys-
tems. The purely physical systems have considerable merit,
because no chemicals are required and no noxious by-prod-
ucts are formed.
VI. CHLOROFLUOROCARBONS AND
OZONE DEPLETION
Chlorofluorocarbons were devised as nonflammable, non-
toxic, noncorrosive alternatives to refrigerants, such as sul-
fur dioxide, ammonia, and chloromethane.130 Their uses
grew to include blowing agents for foam insulation, aerosol
propellants, and solvents for cleaning electronic parts.131
Typical compounds are the following:
Compound Designationa
CFCl3 CFC 11
CF2Cl2 CFC 12
CF2ClCCl2F CFC 113
a
The first number for the chlorofluoromethanes is the number of hydro-
gen atoms plus one, the second the number of fluorine atoms, the re-
maining atoms being chlorine.132
Unfortunately, these compounds were found to destroy
stratospheric ozone.133 This is the layer that protects us
from ultraviolet light. Without it, or with less of it, there
will be more skin cancers and cataracts. The decline has
been worldwide, but most significantly in the polar regions.
The ozone hole in Antarctica was 25 million km2 in
September 1998 (i.e., 2.5 times the area of Europe). 134
Ozone levels at the North Pole have fallen 40% since
1982.135 A 15-year study shows an increase in the wave-
lengths that can damage DNA of 8% per decade at 40-de-
grees north latitude, the latitude of Philadelphia, Pennsyl-
vania and Madrid, Spain.
An international agreement to phase out the use of chlo-
rofluorocarbons was reached in 1990 in Montreal.136 It
The Chlorine Controversy
seems to be working, for tropospheric anthropogenic chlo-
ride has peaked and is now decreasing.137
The search for drop-in replacements for refrigerants has
focused on hydrochlorofluorocarbons and hydrofluorocar-
bons.138 Typical ones are:
Compound Designation
CHClF2 HCFC 22
CH2F2 HFC 32
CH2FCF3 HFC 134a
CH3CClF2 HCFC 141b
CH3CF2H HFC 152a
duPont is doubling its capacity for the last one.139 ICl is ex-
panding its plant for HFC 134a.140 Matsushita Electrical In-
dustrial Co. has opted for a 23:25:52 blend of difluo-
romethane–pentafluoroethane–1,1,1,2-tetrafluoroethane as
a refrigerant.141 If the ozone-depleting potential of CFC 11
is assigned a value of 1.0, then HCFCs have values from
0.01 to 0.11, HFCs 0.0, methyl chloroform 0.1, and carbon
tetrachloride 1.1.136 Although HFCs do not deplete the
ozone layer, they are powerful greenhouse gases. (The most
potent greenhouse gas known is sulfur hexafluoride, of
which 85,700 tons is now in the atmosphere.142 Recom-
mendations for decreasing its use include not using it to fill
tires, sports shoes, and sound-insulating windows; to degas
aluminum, to blanket magnesium; and to use thermal de-
struction for any that is emitted by the electronics industry.)
Since none of these is completely innocent, they too will be
phased out over a period of years.143 Hydrochlorofluoro-
carbon-123 (CHCl2CF3) caused liver disease in nine work-
ers when a leak developed at a smelting plant in Belgium.144
There is also concern about the trifluoroacetic acid that can
be formed from their degradation in the atmosphere and its
effect on wild life when it falls back to earth in a rain.145
These compounds are usually prepared by addition of
hydrogen fluoride to a double bond or by the replacement
of chlorine by fluorine in the presence of a metal fluoride
catalyst.146 The trick is finding the catalyst and conditions
that will give the desired selectively in high yield. An out-
standing example is (3.1):
A1F
CH2 FCCl2  HF →3
(3.1)
CH3CFCl2 99.5% yield
Tri- and tetrachloroethylene can be used as starting materi-
als (3.2, 3.3).147
Cl2CFCCl2  HF→ Cl2CHCCl2F
HF
→ Cl2CHCClF2
(3.2)
| HF
↓ fluxes.153 Propylene carbonate and -butyrolactone have
Cl2CHCF3
55
HF
ClCHFCCl2 beta-CrF
  → CF3CH2F
3
(3.3)
HFC 134a
The catalyst for the first set of reactions (3.2) was a mixture
of antimony pentachloride and titanium tetrachloride.
These sequences may involve addition–elimination reac-
tions, as well as nucleophilic substitution.
The first use of chlorofluorocarbons to be banned was
that of an aerosol propellant. These were used in cosmet-
ics and paints. Other pressurized gases can be used, al-
though propane is really somewhat too flammable for this
use. A fingertip pump or a squeeze bulb can also be used
to provide the pressure to produce the aerosol spray. One
can use a rub-on stick deodorant. A shaving brush can be
used. Chlorofluorocarbons have also been used in prepar-
ing polymer foams, especially for insulation. Other gases,
such as nitrogen, argon, carbon dioxide, pentane, or the
like, can be used instead, but may not be as soluble in the
polymers being foamed.148 Dow Chemical replaced chlo-
rofluorocarbons with carbon dioxide in the preparation of
foamed sheets of polystyrene.149 Another system pre-
froths a mixture of a di- or triacrylate and an acrylated
urethane oligomer with air, then cures it with an electron
beam to form a cellular material.150 Chemical blowing
agents, such as azodicarbonamide can be used. In making
polyurethanes, the presence of a little water will generate
carbon dioxide from the isocyanate to foam the material.
The insulating value of these gases may not be as high as
that of the chlorofluorocarbons, so that thicker layers
might have to be used. Eventually, the gas will diffuse out
of the polymer and equilibrate with the surrounding air. If
this happens in a short time period, then there is little ad-
vantage in using the chlorofluorocarbon. If it happens in
100 years, a system of recovering insulation from used
appliances could be set up to prevent release of the gases
to the atmosphere. The answer is probably somewhere in
between. Another system to produce carbon dioxide for
foaming polymers is to decarboxylate a maleic anhy-
dride–styrene copolymer with a potassium hydroxide
catalyst.151
Many options are being explored for cleaning electronic
parts and such without using chlorofluorocarbons such
as 1,1,2-trichloro-1,2,2-trifluoroethane (HCFC-113).152
These include perfluorocarbons, aqueous detergents, ter-
penes, alcohols, ketones, plasma cleaning, laser cleaning,
and chlorocarbons in zero-emission equipment. The alco-
hols and ketones would have to be used in explosion-proof
equipment. The best approach is to use manufacturing
methods that leave no residues in the first place (i.e., work-
ing under nitrogen or argon) and with no-residue soldering
been effective in removing cured photoresist in the printed
56
circuit board industry, where chlorofluorocarbons were
formerly used.154
The phasing out of chlorofluorocarbons means that
there are now stocks that need to be disposed of in a harm-
less way. Japan has 600,000 metric tons awaiting dis-
posal.155 Hitachi has a catalytic system for burning these
and absorbing the acidic gases in a solution of lime. Burn-
ing in a lime kiln gives 99.9999% destruction.156 Chloro-
carbons can be burned completely using a copper(l) chlo-
ride–potassium chloride on silica catalyst at 400°C.157 The
halogen atoms can also be removed by treatment with
sodium in liquid ammonia at room temperature.158 Sodium
vapor in a flame at 1000°C also destroys chlorofluorocar-
bons.159 Burdenic and Crabtree have devised a method that
uses sodium oxalate at 270°C (3.4).160
CF2Cl2  2 Na2C2O4 270°C
→ 2 NaF
(3.4)
 2 NaCl  4 CO2  C
The best system for dichlorodifluoromethane appears to be
conversion to a useful hydrofluorocarbon (3.5).161 This can
also be done by electrolysis using lead electrodes with
92.6% selectivity (3.5).162
H2
CF2Cl2 Pd
→ CF2H2
/C
70–90% selectivity
CFC-12 HFC-32 (3.5)
Perfluorocarbons are 6,000–25,000 times as potent as
carbon dioxide in producing global warming.163 The
largest single source is the aluminum industry, which re-
leases 28,000 metric tons of perfluoromethane and 3,200
metric tons of perfluoroethane into the world’s air each
year. Aluminum metal is produced by the electrolysis of
trisodium hexafluoroaluminate.164 The process uses 15 kg
fluoride per metric ton of aluminum, of which 10–25% is
lost. Research is being done on new types of electrodes in
an effort to reduce this. A protective cathode coating made
from titanium diboride and colloidal alumina reduces ero-
sion of the cathode and creates higher current efficiency.165
This saves energy and may reduce the production of per-
fluorocarbons. Perfluoromethane can be converted to the
useful monomer, tetrafluoroethylene, in a carbon arc, but
the selectivity needs improvement.166 Some perfluo-
roethane is used for etching semiconductor materials and in
plasma cleaning of chemical vapor deposition cham-
bers.167 The material in the off gases can be destroyed
(99.6%) in a microwave plasma with oxygen and natural
gas in milliseconds.168 This requires a scrubber because HF
and COF2 are among the compounds formed. An alterna-
tive method uses a membrane to remove nitrogen before
burning the concentrated stream at 900°C.169
Chapter 3
Bromine-containing compounds, called halons, were
developed as nontoxic, noncorrosive fire extinguishers.
The two most commonly used ones are bromochlorodiflu-
oromethane (halon 1211) and bromotrifluoromethane
(halon 1301), which have ozone-depleting potentials of 4
and 16, respectively.170 They are used in airplanes, li-
braries, and computer installations, where the use of water
could be damaging. Only about 5% of that released is actu-
ally used in fires. The rest is released in testing. Clearly, a
better method of testing is needed. Atmospheric levels of
halons were still rising in 1998.171 Finding a drop-in re-
placement is proving to be difficult.172 The best course of
action is to blanket the fire with an inert gas, such as carbon
dioxide or nitrogen, in cases where there is no danger of
hurting people. One worker died and another 15 were in-
jured when a fire suppression system that used carbon
dioxide malfunctioned during maintenance at the Idaho
National Engineering and Environmental Laboratory.173
Another worker died of nitrogen asphyxiation at a Union
Carbide plant in Louisiana.174
Methyl bromide is a major source of bromine in the at-
mosphere. It is about 50 times as efficient as chloride in de-
pleting ozone.175 It is used as a soil and crop fumigant. It is
degraded rapidly by soil bacteria, but much of it still es-
capes.176 Adding organic wastes, such as composted ma-
nure reduced losses by 12%.177 To minimize volatilization,
it should be injected at great depths in moist soil under a
tarp with the soil surface packed before and after applica-
tion.178 One of the best barriers consists of two layers of
polyethylene with a layer of an ethylene–vinyl alcohol
copolymer in between. An ammonium thiosulfate fertilizer
also reduces the emissions.179 When used as a fumigant180
for grain, it can be recovered on carbon for reuse, stripping
being done by electrical heating.181 Countries agreed to cut
its usage by one-fourth by 2001 and by half by 2005.182
Since then, the first date has been extended to 2005 in the
United States.183 The timing has been the subject of con-
siderable debate. Farmers say that there is no single eco-
nomically viable alternative available. On the other hand, a
United Nations study concluded that alternatives184 are al-
ready available for nearly all of its uses.185 Integrated pest
management may reduce the need for it. For example, crop
rotation can control some nematodes without the need for
chemicals.186 A new method kills insects in grain with mi-
crowaves as the grain flows from the elevator bucket into
storage.187 Lowering the temperature of stored grain to
65°F can control some pests and is less expensive than fu-
migation.188 Raising the temperature to 122°F in combina-
tion with diatomaceous earth killed 98% of red flour bee-
tles.189 Storage of grain under nitrogen or carbon dioxide
also eliminates insects. Food irradiation is another alterna-
The Chlorine Controversy
tive to the use of methyl bromide.190 (For more on insect
control, see Chap. 11.)
Most work on the replacement of the chlorofluorocar-
bon refrigerants has focused on drop-in replacements for
existing equipment.191 With items for which the stock turns
over every few years, it is reasonable to use nonfluorine
compounds. Ammonia is still used in large refrigeration
units. It could be put into home refrigerators if a sensor to
warn of leaks were included. Such sensors do exist. This
would mean building a unit without copper tubing and with
the use of seals resistant to ammonia. Small amounts of am-
monia are not particularly harmful, as shown by the use of
household ammonia to clean glass windows. Bosch–
Siemens, the largest manufacturer of refrigerators in the
world, is now using a propane–isobutane mixture as the re-
frigerant in Europe. Although the gas is flammable, it
should pose no more of a problem than having a gas stove
in a home. Five million such refrigerators were in use in
1996, with not a single fire having been reported. Presum-
ably, a gas odorant is included or an instrumental sensor for
the gas is built in.192 It is illegal to use hydrocarbon refrig-
erants in home refrigerators in the United States.193 Hydro-
carbon refrigeratants have been used in 200,000 cars in the
United States without a single incident.194
Absorption refrigerating systems, such a gas refrigera-
tor, use ammonia/water and lithium bromide/water as the
refrigerants. These units are compact, noise- and vibration-
free, and simple. They do require more energy. Perhaps this
can be offset by more insulation.195 Solar energy is one
source of heat for them. Cooling can also be done by pass-
ing an electrical current through a junction of dissimilar
metals, the Peltier effect.196 Refrigerators based on this
principle are rugged, reliable, contain no moving parts, and
are low cost, but they consume more energy. Some metals
become hot when magnetized and cool when demagne-
tized, the magnetocaloric effect. An alloy of aluminum, er-
bium, and dysprosium is an example. If cheaper materials
can be found, this could eliminate the need for refrigerants
altogether.197 A refrigerator using gadolinium, containing
varying amounts of silicon and germanium, has been tested
for a year.198 These are also being tested in air conditioners
for cars. Theromacoustic refrigeration is possible using in-
tense sound (200 db) in a compressor that has no moving
parts. The sound outside the device is not loud.199 In coun-
tries in the temperate zone, it may be possible to cut the
amount of energy needed for the household refrigerator by
circulating outside air through its shell in the winter or even
on cool summer evenings. Some hotels in Chicago used the
air from the city’s network of underground tunnels for
cooling until visitors complained of musty odors. They
should be able to go back to this by running the air over ac-
57
tivated carbon to remove the odors. Passive solar heating
and cooling could remove the need for a lot of air condi-
tioning in homes. In cooler climates, such as in New Eng-
land, it probably is not necessary to have an air conditioner
in one’s car. (Energy usage is discussed in Chap. 15.)
VII. CHLORINATED SOLVENTS
Chlorinated solvents replaced more flammable hydrocar-
bon and other solvents. They have often been chosen for
their stability, ease of drying, and their ability to remove
oils. Unfortunately, they can cause cirrhosis of the liver and
in some cases cancer. Efforts are being made to find re-
placements for methylene chloride, chloroform, carbon
tetrachloride, methyl chloroform, and others. Degreasing
with trichloroethylene is still common and dry cleaning of
clothing with perchloroethylene is still the standard. (The
most common organic contaminants in ground water at
hazardous waste sites are trichloroethylene and per-
chloroethylene.200) Better containment is one approach. As
mentioned in Chapter 1, completely enclosed vapor clean-
ers are now available in Germany for use with
trichloroethylene.201 In Dover, Delaware, Capitol Cleaners
reduced its use of perchloroethylene 96% by putting in a
new closed loop system.202
A better approach is to find alternative methods of
cleaning that do not use chlorinated solvents.203 As men-
tioned in Sec. VI, under the use of chlorofluorocarbons
for cleaning, these include aqueous detergent systems,
sometimes augmented by high-pressure jets or ultra-
sound,204 blasting with with particles of ice,205 laser
cleaning,206 plasma cleaning, or other means.207 Commer-
cial units for cleaning clothes with supercritical carbon
dioxide are now available.208 (See Chap. 8 for more on
the use of supercritical carbon dioxide.) In addition, reex-
amination of the process may lead to elimination of the
contaminant oil in the first place. Aqueous-based cutting
oils for machining would be one example.209 A corrosion
inhibitor may have to be present. Water remaining after
rinsing can be removed with jets of air or by centrifuga-
tion. Coating a tungsten carbide cutting tool with a
nanolayer of tungsten plus tungsten disulfide eliminates
the need for any cutting oil.210
Ethyl lactate has been suggested as a relatively nontoxic
biodegradable solvent that is inexpensive. It can be made
from renewable materials by a new fermentation pro-
cess.211 Photoresists and organic contaminants can be
removed with ozone in water in a process that uses no
acids, hydrogen peroxide, or high temperatures while sav-
ing water.212
58
Dry cleaning with perchloroethylene is used with cer-
tain fabrics of silk, wool, or rayon that might shrink in the
usual laundering in hot water. Recent studies have shown
that it can be replaced with “multipurpose wet cleaning.”213
This uses soaps, gentle washing, steam treatment and,
sometimes, microwave drying. Bad stains are removes by a
concentrated detergent pretreatment. Delicate fabrics may
receive handwashing. The process is said to work on cloth-
ing of silk, wool, rayon, and cotton. Most fabrics of cotton
or wool are treated with shrink-proofing reagents today
anyway. Wash-and-wear garments that do not need dry
cleaning are common today. They can also eliminate the
need for energy- and time-intensive ironing of the garment.
Methylene chloride is a common ingredient of paint
strippers. On a house, an alternative is to heat with a heat
gun, then scrape off the paint with a putty knife. Other sol-
vents are needed for stripping finishes from furniture. Epi-
demiological work suggests that methylene chloride can
cause cancer of the liver, bile duct, and brain.214 It is possi-
ble that a professional furniture refinisher could be hired to
remove the finish by ultrasonic cleaning or bombardment
with particles. Further work is needed.
It is now possible to polymerize isobutylene to butyl
rubber in toluene instead of the usual chloromethane.215 A
new titanium sandwich catalyst does the trick. European
manufacturers are phasing out some chloroparaffin lubri-
cants.216 In Japan, rubber is being chlorinated in water in-
stead of carbon tetrachloride.217 This still involves chlo-
rine, but does get rid of the solvent. 1,2-Dimethoxyethane
is being used as an alternative to chlorinated solvents for
the Schmidt Reaction for conversion of an ester to an amine
through an acid azide and a carbamate (3.6).218 This elimi-
nated accidents from polyazides made in situ from methy-
lene chloride or chloroform.
NaN CH 3OH
RCOOCH3 
 →3
RCON3  
→
CH3SO3H
(3.6)
RNHCOOCH3→RNH2
3.13
Chapter 3
Photocatalytic titanium dioxide coatings can be self-
cleaning, converting organic materials, such as bacteria
and dirt, to carbon dioxide at practical rates at room tem-
perature.219 This offers the possibility of self-cleaning
buildings and windows.
VIII. SYNTHESES WHERE THE CHLORINE
IS NOT IN THE FINAL PRODUCT
Frequently, the chlorine is not in the final product. Instead
it is in by-product hydrogen chloride or salts. Workers at
Flexsys (formerly Monsanto) have devised some syntheses
that obviate the need for chlorine (3.13–3.14).220 In each
case, the traditional process is shown first.
The benzamide formed in the second example (see 3.13)
is recycled to the process. It is also possible to use aniline
in place of the benzamide in a process that produces 74%
less organic waste, 99% less inorganic waste, and 97% less
wastewater.221
In one case, the halogen is generated in situ by electrol-
ysis so that none appears in the final product and none is
lost (3.15).222
The yield with sodium bromide is 89%, with sodium chlo-
ride 6%. If this process is general for olefins and if the toxic
acetonitrile can be eliminated, this could become an impor-
tant way to eliminate by-product salts in the preparation of
epoxides. As mentioned in Chapter 1, propylene oxide is of-
ten made by adding hypochlorous acid to propylene, then de-
hydrohalogenating with base.223 The alternative process that
uses the oxidation of ethylbenzene with oxygen to form the
hydroperoxide followed by transfer of an oxygen to propy-
lene is gaining in popularity. Direct oxidation of propylene
with oxygen to give propylene oxide can be highly selective
at low conversions (e.g. 99% selective with a gold/titanium
dioxide catalyst at 1–2% conversion).224 A EuCl3 /Zn/acetic
acid system was 94% selective at 3% conversion.225 The
The Chlorine Controversy
3.14
3.15
3.16
3.17
challenge is to obtain high selectivity at nearly complete con-
version. A membrane reactor that removed the propylene ox-
ide continuously as formed might help.
Halogens can also be generated in situ by the action of
an oxidizing agent on a sodium halide.226 In this example
(3.16), the oxidizing agent is potassium peroxymonosulfate
(Oxone). The reactions were run in water diluted with ace-
tone, ethyl acetate or carbon tetrachloride. Bromine can
59
also be generated in situ by the action of sodium perborate
on sodium or potassium bromide.227 Such processes elimi-
nate the dangers inherent in handling and storage of the
halogens, but not any toxicity associated with the halogen-
containing products.
The Heck reaction has been improved so that the usual
halogen salts are not formed, and no phosphine ligands are
required (3.17).228 However, a toxic gas is formed.
60
IX. SUMMARY AND CONCLUSIONS
Greenpeace called for a ban on the use of chlorine and its
compounds. The industry responded with “a combination
of anger, indignation and denial.”229 Companies came to-
gether to mount a public information campaign. Why
should the two sides take such extreme positions? Green-
peace has learned that a carefully thought-out analysis of a
problem may attract little attention from the public or the
media. However, taking an extreme position and carrying
out highly visible stunts can. This group hung a banner high
up on the multistory duPont Building in Wilmington,
Delaware at the time of the annual shareholders meeting.
The banner protested duPont’s production of chlorofluoro-
carbons. The industry is large and profitable, with many
paid-off plants. It does not want to see its business wiped
out. It does not want to spend money to change unless there
is compelling evidence forcing it to do so.
Many chlorine compounds are active biologically.
Some, such as the polychlorinated dibenzo-p-dioxins, are
extremely potent. Many of the problems with some of these
compounds are worldwide. Ozone depletion by chlorofluo-
rocarbons is an example. Chlorine compounds do not nec-
essarily stay where you put them. The widely used herbicide
atrazine (3.18) is now widely distributed in ground water.
Germany, Italy, and the Netherlands have limited its use.1
Long-range transport on winds is bringing chlorinated pes-
ticides to places as remote as the Arctic island of Svalbard,
Norway.230 In a sample of 450 polar bears from this local-
ity, 7 had both male and female genitals.231 It has been esti-
mated that the use of chlorinated pesticides could be re-
duced by two-thirds with only marginal influence on
farmers, just by changing tilling and cultivating practices.1
Although many highly chlorinated insecticides, such as
DDT, have been outlawed in the developed nations, they are
still used in other parts of the world. Thus, there is a need for
making the ban global. We have also come to realize that a
chemical need not kill an animal outright to wipe out a pop-
ulation. This can happen by altering behavior patterns or re-
productive success. If male animals are feminized so that
they do not breed successfully, or if females take no interest
in their young and do not provide them with food, or if ani-
mals lose the ability to find and capture prey, the species will
not survive. Nor will the species survive if it loses the be-
3.18
Chapter 3
havior that helps it avoid predators. The thinning of egg
shells threatened to wipe out species of several predatory
birds, such as ospreys, eagles, peregrine falcons, and brown
pelicans. All of this means that new chlorine compounds
and others for release into the environment will have to be
screened more thoroughly. There is also the nagging ques-
tion of how much of what is seen in animals will be appli-
cable to humans. This means finding ways to screen for the
cancers that may take 30 years to develop. Fortunately, the
two sides in the controversy, plus government, are now in
agreement that more research is needed and money is be-
coming available for it.
Chlorinated solvents might be handled by simple con-
tainment. The deadly dioxins might be removed from stack
gases with the BASF device, or 2% nitrilotriacetic acid
might be added to prevent their formation.232 A membrane
with a prefilter could be used to remove natural organic
matter from drinking water before treatment with chlorine
to reduce the formation of unwanted by-products, such as
chloroform. Systems might be set up to segregate chlorine-
containing plastics out of waste going into incinerators.
This would be very difficult with film used to package
food. Chlorinated polymers could be banned from such ap-
plications. Their use might also be lessened by adding a
tax. The possibility of loss of dangerous reagents, such as
chlorine or phosgene during shipment or storage, could be
reduced greatly by generation on site as needed. About half
the chlorine used ends up in by-product hydrogen chloride
and salts that may present a disposal problem. Recent im-
provements to the Deacon process for converting hydrogen
chloride back to chlorine with oxygen in the presence of
copper chloride may help reduce this problem.233 If every
plant were independent, then, in theory at least, each could
electrolyze aqueous solutions of its waste sodium chloride
back to chlorine and sodium hydroxide for reuse. The real
value of the current chlorine controversy may be in getting
companies to rethink their entire processes from start to fin-
ish.234 As waste disposal costs rise, there should be greater
incentive to devise chlorine-free processes.
A German study found that about half of the 2.9 million
metric tons of chlorine used there annually could be elimi-
nated at a net cost increase of only 1%.235 Eighty percent of
the chlorine used in Germany goes into propylene oxide,
epoxy resins, polyvinyl chloride, and phosgene. Propylene
oxide can be made by oxidation of propylene with hydro-
gen peroxide or hydroperoxides at lower cost. Diphenyl
carbonate can be used to replace phosgene in the prepara-
tion of polycarbonates (see Chap. 2) It may be possible to
replace the use of phosgene in making isocyanates for
polyurethane resins. Up to 50% of the polyvinyl chloride
could be replaced, mainly with polyolefins. [Polypropylene
with the properties of plasticized polyvinyl chloride is now
The Chlorine Controversy
available.236] Houses can be covered with wood, alu-
minum, brick, stucco, and so forth; as well as with
polyvinyl chloride. Sewer pipes can be made of polyethy-
lene as easily as from polyvinyl chloride. Some cities in
Germany and Austria have banned the use of polyvinyl
chloride.1 Epichlorohydrin is used to react with bisphenols
in the preparation of epoxy resins. There are other ways of
making bisepoxides (e.g., oxidation of olefins with hy-
droperoxides). Elf Atochem sells limonene dioxide, epoxi-
dized poly(1,3-butadiene), and epoxidized vegetable oils
that may be made by such a route and that might then be
made into epoxy resins.237 This would require some exper-
imentation to develop epoxy resins with properties that
matched or exceeded the properties of the current favorites.
The controversy has not hurt business for the chlorine
industry, which is booming.238 There have been some
shifts in the product line. Methylene chloride demand is
dropping. More trichloroethylene is being produced as a
feedstock for fluorocarbon production. More sodium chlo-
rite is being produced as a precursor for chlorine dioxide to
be used in the bleaching paper. The trend should start
downward in the future as chlorine-free alternatives are
found and as ageing plants are retired.
Although many chlorinated compounds are destined to
remain in the market for a long time, society does owe a
debt of gratitude to environmental organizations such as
Greenpeace and the World Wildlife Fund (with which
Theo Colborn is associated) for calling attention to prob-
lems that may not have been evident to others. Their call
has caused funding on the problems to be increased.
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Chlorinated Solvents for Cleaning and Degreasing, U.S.
Environmental Protection Agency, Washington, D.C.,
EPA/625/R-93/016, Feb. 1994; (b) D. Pendick, New Sci.,
Sept. 10, 1994, 21.
204. (a) H. Stromberg, Rubber World, 1995; 212(5), 14; (b)
Chem. Eng., 1997, 104(11), 107.
205. Pollut. Equip. News, Aug. 1998, 16; Equipment from Ice
Cleaning Systems, Indianapolis, Indiana.
206. (a) V. Leclair, Environ. Sci. Technol., 1997, 31, 215A; (b)
S.H. Lusi, Chemtech, 1998, 28(6), 56.
207. P.M. Randall, Engineers’ Guide to Cleaner Production
Technologies, Technomic, Lancaster, Pennsylvania, 1997.
208. R&D (Cahners), 1997, 39(9), 37.
209. D. Klamann, Ullmann’s Encyclopedia of Industrial Chem-
istry, 5th ed. 1990, A15, 480.
210. R. Komanduri, Green Chemistry and Chemical Engineer-
ing Conference, Washington, D.C., June 23, 1997.
211. J. Knight, New Sci., Mar. 21, 1998, 7.
212. (a) Presidential Green Chemistry Challenge Award Recip-
ients. U.S. EPA 744-K-97-003, Sept. 1997, 4; (b) R.R.
Mathews. U.S. patent 5,464,480, 1995.
213. (a) EPA. Summary of a Report on Multipurpose Wet
Cleaning, U.S. Environmental Protection Agency, Wash-
ington, D.C., EPA744-S-94-001, June 1994; (b) H. Black,
Environ. Sci. Technol, 1996, 30, 284A; (c) Environment,
1995, 37(1), 22.
214. J. Huff, J. Bucher, and J.C. Barrett, Science, 1996, 272,
1083.
215. (a) Chem. Ind. (London), 1995, 362; (b) M. Baird and F.
Barsan, J. Chem. Soc., Chem. Commun., 1995, 1065.
216. Chem. Eng. News, June 26, 1995, 14.
217. G.S. Samdani, Chem. Eng., 1995, 102(5), 15.
218. N. Galvez, M. Moreno–Manas, R.M. Sebastian, and A.
Vallribera, Tetrahedron, 1996, 52, 1609.
219. (a) R. Dagani, Chem. Eng. News, July 14, 1998, 14; (b)
W.A. Jacoby, P.C. Maness, E.J. Wolfrum, D.M. Blake,
and J.A. Fennell, Environ. Sci. Technol., 1998, 32, 2650.
220. (a) M.K. Stern, J. Org. Chem., 1994, 59, 5627; (b) R.A.
Sheldon, Chemtech, 1994, 24(3), 38.
221. (a) M.K. Stern, B.K. Cheng, and J. Clark, New J. Chem.,
1996, 20, 259. (b) L.R. Raber, Chem. Eng. News, July 6,
1998, 25.
222. N. Takano, Chem. Lett., 1996, 85.
223. Chem. Eng. News, June 22, 1998, 11.
224. T. Hayashi, K. Tanaka, and M. Haruto, J. Catal., 1998,
178, 566.
225. I. Yamanaka, K. Nakagika, and K. Otsuka, Appl. Catal. A,
1998, 171, 309.
226. R.K. Dieter, L.E. Nice, and S.E. Velu, Tetrahedron Lett.,
1996, 36, 2377.
227. (a) G.W. Kalbalka and K. Yang, Synth. Commun. 1998,
28, 3807; (b) B.P. Bandgar and N.J. Nigal, Synth. Com-
mun., 1998, 28, 3225.
66
228. M.S. Stephan, AJJM Teunissen, GKM Verzijl, and J.G. de
Vries, Angew. Chem. Int. Ed. Engl., 1998, 37, 662.
229. M. Heylin, Chem. Eng. News, Nov. 21, 1994, 5.
230. M. Oehme, J–E. Haugen, and M. Schlabach, Environ. Sci.
Technol., 1996, 30, 2294.
231. C. Holden, Science, 1998, 280, 2053.
232. R. Addink, R.H.W.L. Paulus, and K. Olie, Environ. Sci.
Technol., 1996, 30, 2350.
233. (a) H.Y. Pan, R.G. Minet, S.W. Benson, and T.T. Tsotsis,
Ind. Eng. Chem. Res., 1994, 33, 2996; (b) E. Wilson,
Chem. Eng. News, Sept. 11, 1995, 9.
234. R. Lundquist, Chem. Eng. News, Nov. 28, 1994, 3.
235. G.S. Samdani, Chem. Eng., 1995, 102(2), 13.
236. (a) D.E. Mouzakis, M. Gahleitner, and J. Karger–Kocsis, J.
Appl. Polym. Sci., 1998, 70, 873; (b) Y. Hu, M.T. Krejchi,
C.D. Shah, C.L. Myers, and R.M. Waymouth, Macro-
molecules, 1998, 31, 6908.
237. Elf Atochem, 1996 trade brochure.
238. (a) E.M. Kirschner, Chem. Eng. News, Jan. 9, 1995, 11; Jan.
1, 1996, 12; (b) B. Hileman, J.R. Long, and E.M. Kirschner,
Chem. Eng. News, Nov. 21, 1994, 12; (c) P.L. Layman,
Chem. Eng. News, May 6, 1996, 22; (d) Chem. Eng. News,
July 17, 1995, 30; (e) N. Botha, Chem. Ind. (London), 1995,
832; (f) Chem. Eng. News, Oct. 16, 1995, 8; (g) Chem. Eng.
News, Apr. 22, 1996, 19; (h) M.S. Reisch, Chem. Eng.
News, Feb. 13, 1995, 15; (i) P.M. Morse, Chem. Eng. News,
Oct. 20, 1997, 19; (j) M. McCoy, Chem. Eng. News, Sept. 7,
1998, 17; Nov. 23, 1998, 26; (k) C. Martin, Chem. Brit.,
1997, 33(5), 44; (l) M. Beal, Chem. Ind., 1997, 434.
RECOMMENDED READING
1. G. Graff, Technol Rev 1995, 98(1), 54; the chlorine contro-
versy.
2. G.W. Gribble, Environ Sci Technol 1994; 28, 310A; review
of natural chlorine compounds.
3. D. Henschler, Angew. Chem. Int. Ed. Engl 1994; 33, 1920;
toxicity of chlorine compounds.
4. B. Hileman, J.R. Long, and E.M. Kirschner, Chem. Eng.
News, Nov. 21, 1994, 12–26; uses of chlorine compounds
and the controversy.
5. R. Stone, Science, 1994, 265, 308; estrogen mimics and the
chlorine controversy.
6. E. Ayres and H. French, World Watch, 1996, 9(5), 15;
propane/isobutane blends in European refrigerators.
Chapter 3
EXERCISES
1. Look up the fish advisories in your area to see how
many are due to polychlorinated biphenyls and
other chlorinated compounds.
2. In your laboratory work for the past month, how
many times have you run substitution reactions on
halides or produced waste halide salts? In looking
back on the work, can you think of alternatives
that would avoid the use of halogens?
3. How does your city disinfect its drinking water
and its treated wastewater?
4. Are there any places in your areas where the
groundwater is contaminated with trichloroethy-
lene, perchloroethylene, chlorinated herbicides, or
chlorinated insecticides? If so, do any of them re-
quire treatment?
5. Where is dioctyl phthalate used as a plasticizer?
Devise a copolymer made with a plasticizing
comonomer that would eliminate the need for the
phthalate.
6. Compare the properties of the newer polyolefins
made with metallocene (Adv Polym Sci 1997;
127:143) and Brookhart catalysts with those of
plasticized polyvinyl chloride.
7. Compare the properties of epoxy resins based on
bisphenol A–epichlorohydrin with those based on
epoxides that can be made without the use of
epichlorohydrin.
8. Devise a potentially commercial method of
preparing aluminum by electrolysis that does not
involve any fluoride.
9. Visit the local supermarket and hardware store.
See how many items are marked with the
polyvinyl chloride symbol.
10. How could polyvinylidene chloride barrier coat-
ings in food packaging be replaced? If you have
trouble coming up with an answer, see G. Ondrey.
Chem Eng 1998; 105(1):29; and H.C. Silvis.
Trends Polym Sci 1997; 5(3):75.
4
Toxic Heavy Metal Ions
I. THE PROBLEM
The toxicities of heavy metal ions are well known.1 These
include cadmium, chromium, cobalt, copper, lead, mer-
cury, tin, and zinc. For convenience, nonmetals such as ar-
senic, asbestos, and selenium are also included here. Mer-
cury-containing wastes dumped into Minamata Bay in
Japan killed hundreds of people and sickened many more.2
Hundreds of deaths also occurred in Iraq when people ate
grain treated with an organomercury biocide intended to
protect the young seedlings from fungi.3 The expression
“mad as a hatter” originated with hatters poisoned with the
mercury compounds used in the felting of hats. Some au-
thors have postulated the poisoning of modern man from
silver amalgam dental fillings, much as lead poisoning
from the use of lead cooking and storage vessels may have
led to the decline of the Roman empire.4 In 1995, fishermen
in the United States were advised not to eat the fish that
they caught in 1306 different bodies of water because of the
mercury in them.5 This figure should be compared with
438 advisories for polychlorinated biphenyls, 122 for
chlordane, 52 for dioxins, and 35 for DDT. Game fish may
accumulate mercury to 225,000 times the concentration in
the surrounding water.6 There is enough mercury in the
Florida Everglades to poison some wading birds that feed
on fish.7 The amount of mercury that people should be al-
lowed to eat in fish is a matter of current debate.8
Hundreds of people in Japan suffered from a degenera-
tive bone disease called itai-itai because they drank water
containing cadmium.9 They lived downstream from a mine
and smelter that produced zinc and cadmium. In West Ben-
gal, India, where 800,000 people drink well water contain-
ing over 50  /L arsenic, 200,000 people developed skin le-
sions from drinking the water.10 In Bangladesh, 70 million
people drink well water containing arsenic.11 The problem
67
arose when international agencies drilled deeper wells to
avoid contaminated surface water, but did not test the wa-
ter. Too much arsenic in drinking water is known to result
in more deaths from cancer.12 In a region in northern Chile,
arsenic-containing water caused highly elevated rates of
lung and bladder cancers.13 Selenium can also be bioaccu-
mulated. Waterfowl in refuges in the western United States
have been poisoned by agricultural drainage from selenif-
erous soils.14
Contamination of the environment with toxic heavy
metals began long ago. Evidence of the Roman use of cop-
per and lead can be found in ice cores from Greenland and
in cores of European bogs.15 Mining of gold and silver has
left a legacy of mercury at mining sites.16 The Carson River
Superfund site in Nevada is estimated to release 150–400
kg / year of mercury, which is comparable with the 300
kg / year released by a 1000-MW coal-fired power plant.
Mercury vapor can persist in the atmosphere for as much as
a year. Households can also be sources of metals.
Tetraethyllead was used as an antiknock agent in gasoline
for about 50 years. It has now been banned in the European
Union and in North America because it can lower the IQ of
children.17 Harmless titanium dioxide has replaced basic
lead carbonate as a white pigment in paint. As a result of
these two uses, unacceptable levels of lead persist in some
soils and older houses. In England, roughly 60% of the cop-
per in the sewage came from the plumbing in houses.18
Galvanized tanks accounted for 50% of the zinc in the
sewage system. Highway runoff in Ohio contains zinc and
cadmium from tire crumbs; copper and lead from brake
dust; zinc, chromium, copper, and magnesium from en-
gines; as well as oil and grease.19
The form or valence of the metal can make a big dif-
ference in its toxicity. The tin plate on a food can is es-
sentially harmless. Yet, tributyltin derivatives are used to
68
kill barnacles on ships. Mercury amalgam fillings for
teeth are relatively harmless, although there is some de-
bate on their effects over long times (as mentioned ear-
lier). On the other hand, a Dartmouth professor died after
getting a couple of drops of dimethylmercury on gloves
that allowed it to penetrate to her skin.20 Chromium(VI)
is carcinogenic, but chromium(III) is an essential element
for human nutrition. Chromium, cobalt, copper, fluoride,
manganese, and zinc are among the 27 elements essential
for humans. The metal ions are often found in enzymes.
The amounts required may be small. The average adult
human contains about 2–3 g of zinc.21 It is easy to be
overdosed with materials such as zinc, fluoride, or even
iron, if there is too much in the diet or in the drinking wa-
ter. People who take large amounts of dietary supple-
ments are at the most risk. If a metal compound has a very
low solubility in water and in body fluids and is not
volatile, then it may not be a problem at all. Much work
has been done to determine the speciation of metals in
soil, water, combustion gases, and such.22 Nickel is also
carcinogenic, apparently by catalyzing the oxidation of
bisulfite ion to monoperoxysulfate ion, which is then con-
verted to sulfate radical which, in turn, attacks the DNA.23
Nickel in jewelry is the most common cause of contact al-
lergies in several European countries.24 Arsenic, cad-
mium, lead, and mercury are more toxic than the other
foregoing metals and are not essential for humans.
The reader would do well to check the extent of con-
tamination by toxic heavy metal ions of the area where he
or she lives. Delaware will be use as an example to illus-
trate common sources. The Delaware River Estuary is con-
taminated with arsenic, cadmium, chromium, copper, lead,
mercury, and silver.25 The arsenic, chromium, copper, and
lead are largely from point sources. Dredge spoil disposal
is a problem because it contains copper, mercury, and poly-
cyclic aromatic hydrocarbons. The use of sewage sludge as
a soil amendment is limited by the presence of toxic heavy
metal ions. An example is Middletown, Delaware, where
the lead in the sludge originates in a local battery plant.
Zinc is a problem in Red Clay and White Clay Creeks be-
low two vulcanized fiber plants that use zinc chloride to
soften cellulose. Although the releases have stopped, re-
lease of zinc from the sediments in Red Clay Creek keeps
the stream contaminated. The east branch of the Maurice
River above Millville, New Jersey is contaminated with ar-
senic from an agricultural chemical plant upstream.
Tetraethyllead was once made at the Chambers Works of
the duPont Co., across the river from Wilmington,
Delaware. The company is studying phytoremediation by
ragweed and other plants as a means of reducing the lead
content of soils at the plant. The Chloramone Corp. is be-
ing taken to court for releases of mercury from its chlorine
Chapter 4
plant in Delaware City, Delaware.26 Municipal solid waste
from northern Delaware is burned at an incinerator in
Chester, Pennsylvania. Incinerators operating at
1000–1100°C evaporate 98–100% of the cadmium, cop-
per, lead, and zinc so that compounds of these elements end
up in the fly ash, which must then be treated as hazardous
waste.27
Materials containing these metals have been quite use-
ful in many applications in the past. Before examining
ways to prevent pollution from them, their uses must be
considered. The following list has been put together from
the relevant sections in the Encyclopedia of Chemical
Technology, Ullmann’s Encyclopedia of Industrial Chem-
istry, and, for mercury, a paper by Randall:28
Arsenic:
Copper chromium arsenate as a wood preservative
Calcium and sodium arsenate herbicides
Lead arsenate formerly used on fruit crops
Formerly in cotton defoliants
Sodium arsenite in cattle and sheep dips
Alloys with copper and lead for bearings
With aluminum, gallium, and indium in semiconduc-
tors
Gallium aluminum arsenide in solar cells
Gallium arsenide phosphide in light-emitting diodes
Gallium arsenide infrared detectors, lasers, and
photocopiers
Arsanilic acid as a growth additive for poultry and
swine
Arsenic compounds are also by-products of processing
gold and lead ores and of coal combustion.
Asbestos:
Matrix reinforcement in shingles for houses, vinyl
floor tile, brake linings and clutch facings
Insulation
Portland cement
Formerly in gloves and fire suits
Cadmium:
Nickel–cadmium, silver–cadmium, and mercury–
cadmium batteries
Plating
Pigments such the sulfide and selenide
Cadmium laurate with barium laurate as stabilizers for
polyvinyl chloride
Semiconductors, such as the sulfide and selenide, as in
solar cells
Phosphor in television tubes
Brazing and low-melting alloys (e.g., in copper)
Toxic Heavy Metal Ions 69

Some is also released from the burning of coal and the
use of phosphate fertilizers.
Cobalt:
With molybdenum in desulfurization catalysts
Catalyst for the oxo process, p-xylene oxidation, and
such
Electroplating
Salts of fatty acids as driers for paints
Color for glass
Helps rubber adhere to steel tire cord
Formerly a foam stabilizer in beer where it caused
heart problems and some deaths
Chromium:
Electroplating and chromizing steel
Stainless steel
Chromite grain in foundries
Chromium dioxide in magnetic tape
Pigments, such as chromium oxide and lead chromate
Zinc chromate for corrosion protection of cooling
towers, and such
Tanning of leather
Dyeing of textiles
Chromium copper arsenate as a wood preservative
(uses 62% of the chromic acid in the United States)
Catalyst for polymerization of ethylene
Copper chromite catalyst for hydrogenation
Zinc chromate near the zinc anode gives batteries
50–80% more shelf life
Coal combustion is the largest source of chromium in
the environment.
Copper:
Wiring, printed circuits
Plumbing
Roofing
Auto radiators
Coins
Algicide in swimming pools and reservoirs
Fungicides
Electroplating
Solar collectors
Chromium copper arsenate wood preservative
Cuprous oxide in antifouling coatings for ships
Pigments, such as copper phthalocyanine
Lead:
Pipe and cable sheathing
60% of the total goes into lead–acid batteries
14% of the total goes into lead glazes for glass and
china (Lead can leach from pieces that are not fired
properly.29
Stabilizers for polyvinyl chloride
Pigments such as basic lead carbonate (in white house
paint), red lead (in primer paint for steel), lead chro-
mate
Shielding against x-rays
Cathode ray tubes
Chemically resistant linings
Solder
Tetraethyllead antiknock agent for gasoline
Lead shot, ammunition, yacht keels, wheel weights
Sinkers for fishing
Lead shot and sinkers have poisoned waterfowl that
have ingested them.
Mercury:
Fungicide in seed treatment
Slimicide in paper mills
Biocide in latex paints
Dental amalgams
Batteries
Catalysts for transesterification of vinyl acetate as
well as addition to triple bonds
Thermometers and leveling bulbs
Mercury vapor and fluorescent lamps
Electrical switches
Mercury cathode for electrolysis of sodium chloride in
the manufacture of chlorine and sodium hydroxide
Pigments, such cadmium mercury sulfide
Coal burning and incinerators are the largest sources.30
Mercury metal boils at 357°C so that it escapes from the
stacks. Even crematoria are sources, the mercury coming
from the fillings in the teeth.31
Nickel:
Stainless steel
Other alloys with steel and other metals
Electroplating
Coins and jewelry
Nickel–cadmium batteries
Catalysts for hydrogenation
Light stabilizer in polyolefins
Some also comes from burning coal. The smelting of
nickel and copper sulfide ores has resulted in tremendous
air pollution from sulfur dioxide. At one time this could be
detected on white pines (a sensitive species) at a distance of
10 miles from the smelter at Sudbury, Ontario. INCO now
uses a flash smelter which roasts the ore with oxygen in a
70
closed vessel that gives a concentrated stream of sulfur
dioxide and saves half the energy. Thus, 90% of the sulfur
in the ore can be recovered after conversion to sulfuric acid
at the rate of 2300 ton/day. Even at this rate of recovery the
facility will emit up to 265,000 tons of sulfur dioxide in
1996.32
Zinc:
Zinc chromate and phosphate for corrosion protection
Galvanizing
Nickel oxide–zinc batteries
Flaked zinc pigment
Electroplating
Alloys
Zinc dithiocarbamate fungicides and stabilizers
Treating cellulose to make vulcanized fiber
Phosphors
Zinc dithiophosphates in lubricating oils
Zinc oxide in tires
Opaque agent in some sunscreens
Various approaches are being studied in an effort to
eliminate or minimize the problems with the toxic heavy
metals while not doing away with the end uses. These will
be discussed in the following sections. They include (a) al-
ternative nonaqueous methods for which loss in water has
been a problem, (b) the use of other less harmful metal or
organic coatings, (c) use of catalytic, rather than stoichio-
metric, amounts of reagents in chemical processes, (d) use
of a reagent on a support or in a separate phase so that none
is lost, (e) reagents that contain no metal, (f ) development
of sure-fire collection and recycling techniques that do not
allow the item containing the metal to enter the general
waste stream, (g) separation and stockpiling in cases for
which the material is an unwanted by-product, and (h) reg-
ulation, and even banning, if the harm exceeds the benefits.
Cadmium is a by-product of zinc mining. Arsenic is a by-
product of other mining.33 Both may have to be stockpiled.
Organomercury biocides have been banned in latex paints,
seed treatments, and other uses.34 A New Jersey law is try-
ing to lower the mercury content of batteries to 1 ppm. It
also sets up a collection program for spent batteries. Cali-
fornia and Minnesota restrict the disposal of fluorescent
lights (each of which contains 25–50 mg of mercury).
Technology exists for recovery of the mercury in the
lamps.35 A federal law for the United States that would
phase out the use of mercury in disposable batteries has
been proposed.36 The United States Environmental Protec-
tion Agency (EPA) has proposed new standards that will
reduce the emission of mercury from incinerators by 80%
and lead and cadmium emissions by 95%.37 The EPA has
Chapter 4
limited the air discharge of chromium compounds from
decorative electroplating tanks to 0.015 mg / m3 of air.38
The exposure limit for asbestos is 0.1 fiber per cubic cen-
timeter of air.39 The World Health Organization (WHO)
has set the limits on drinking water contaminants at (g/L)
lead 10, nickel 20, copper 2000, boron 300, antimony 5, ar-
senic 10, trihalomethanes 100, bromate 25, atrazine 2, lin-
dane 2, and simazine 2.40 Atrazine and simazine are com-
monly used herbicides for corn, and other crops. Lindane is
a highly chlorinated insecticide. (Agrochemicals will be
discussed in Chap. 11.) Witco Corp. voluntarily stopped
the sale of cadmium-containing heat stabilizers for
polyvinyl chloride on June 30, 1994.41
II. END-OF-THE-PIPE TREATMENTS
It would be preferable to eliminate the sources of these
toxic heavy metal ions. However, in some cases this will be
difficult. The switch from burning coal to generate electri-
cal power to renewable sources of energy to moderate
global warming will take many years. Losses of metal ions
from mining processes such as flotation and hydrometal-
lurgy will continue although perhaps at a reduced rate.42
Surplus cadmium from the mining of zinc and arsenic from
other mining will have to be dealt with. The leaching of ar-
senic and selenium from soils will continue to be problems
unless changes in land use and other practices can reduce
them. It will be necessary to find ways to eliminate them
from effluent air and water.
The gasification of oil in the Shell process leaves the
vanadium and nickel from the oil in the soot ash. Lurgi
has devised a process to recover the vanadium in a form
that can be used by the metal alloys industry.43 The Inter-
national Metals Reclamation Company (a subsidiary of
INCO) operates a facility for the recycling of nickel–cad-
mium batteries in Pennsylvania. “Since 1978, Inmetco has
recycled nearly 1.5 billion lb of material that might other-
wise have been disposed of in landfills.” The recovered
cadmium goes back into new batteries.44 A process recy-
cles batteries containing mercury by heating to 650°C.
The mercury volatilizes and is condensed in a wet scrub-
ber. The residue of zinc, iron, and others can be recycled
to standard smelters.45 Zinc can be removed from galva-
nized steel by vaporization at 397°C/10 Pa.46 Efforts are
being made to extend the technique to removal of tin from
copper wire, copper from circuit boards, and metal from
batteries.
Mercury can be removed from flue gases by adsorption
on activated carbon, with or without iodine or sulfur.47 This
may require cooling the gases, which would be unneces-
Toxic Heavy Metal Ions
sary otherwise. Domestic waste averages about 3–5 g of
mercury per ton. Most of the mercury ends up in the ash
fraction, which must be dealt with separately. Ten percent
sulfur on sepiolite (a silicate) is said to compare well with
sulfur on activated carbon for removal of mercury in gas
streams at 320 K.48 A 4-A molecular sieve containing 1%
silver can be used to clean up natural gas containing up to
300 ppb of mercury.49 Another method uses a hollow-fiber
membrane containing an oxidizing liquid, the mercuric ion
being precipitated later as mercury (II) sulfide.50 An older
method used sulfur on activated carbon.
Metal workers clean up their wastes by a variety of
methods, which include chemical precipitation, elec-
trowinning, and ion exchange.51 Many electroplating firms
are now reducing the amount of wastewater by using the
last rinse of one batch as the first rinse of the next batch.
Chemical precipitation has some problems. If the precipi-
tate is sent to a landfill, the metals in it are thrown away and
may possibly be leached from the landfill. The precipitate
may also be sent off-site to a metals recovery firm. Al-
though, precipitation can lower the metals content to ac-
ceptable levels in favorable cases, some metal ions are still
left in the waste water. Precipitation of mercury as the sul-
fide leaves 11 ppb of mercury in the effluent.52 This is the
process used at the chlor-alkali plant in Delaware City,
Delaware. Since there can be tremendous bioaccumulation
of mercury, this may not be enough to allow the fish in the
river to be eaten. It would be better for the plant to switch
to the well-established “Nafion” (a perfluorinated poly-
meric sulfonic acid made by duPont) membrane process
that requires no mercury.53 Ion exchange does not remove
all the metal ions either. It can be quite slow at low levels
of metal ions. At least, the recovered metal ions can be re-
cycled to the head of the plant. Electrowinning is hard at
very low levels of metal ions. Use of a carbon fiber elec-
trode can help some. Electrolytic fluidized beds are said to
help and to be cheaper than ion exchange.54 Concentration
of the waste water by reverse osmosis before electrowin-
ning would reduce the amount lost. Combining this with to-
tal water recycle would help. If the rinses are concentrated
by reverse osmosis, it may be possible to recycle them to
the process without electrowinning or ion exchange. This
might require analysis of each plating bath before use to as-
sure the proper concentrations of ingredients.
Asarco has devised a method of treating the water from
a lead–zinc mine with sulfate-reducing bacteria that gener-
ate hydrogen sulfide in situ to precipitate the metal ions.55
Arsenic can be precipitated from the effluent of gold ex-
traction as FeAsO42H2O.56 Aluminum-loaded Shirasu ze-
olites can also remove arsenic from water.57 Car-
71
boxymethyl--cyclodextrin can complex cadmium simul-
taneously with organic compounds such as anthracene,
trichlorobenzene, and DDT.58 It is suggested for cleanup of
leachates from sites containing mixed hazardous waste. A
zeolite containing a hexadecyltrimethylammonium salt;
has been used to pick up chromate, molybdate, and selenate
ions from water.59 Chromate ions can be removed selec-
tively in the presence of sulfate, chloride, bicarbonate, and
nitrate ions, with a cross-linked resin containing dipicoly-
lamine copper(II).60 Nalco markets a polymeric chelating
agent (NALMET) that removes copper, lead, nickel, and
zinc ions from wastewater to lower levels than can be ob-
tained by precipitation processes.61 Presumably, the metal
ions can be recovered for reuse. A. Lezzi and co-workers
have devised some polymeric sulfur-containing reagents
(4.1, 4.2) for nearly complete removal of lead and mercury
ions from water.62
polystyreneCH2(OCH2CH2)13NCH2CH2N(CSSNa)2
\
CSSNa (4.1)
polystyreneCH2(OCH2CH2)nOCH2CH2SH (4.2)
The former can reduce lead and mercury ions from 18–19.5
ppm to 0.005 and 0.05 ppm, respectively, in 7 h. The latter
can take mercury ion from 20 ppm to less than 10 ppb in 2
h. Unless much shorter times can be used, these may be im-
practical for commercial use. Microspheres of poly( hy-
droxyethyl methacrylate-co-ethylene glycol dimethacry-
late) containing the aminoazosulfonate dye Congo red,
have been used for removal of cadmium ion from water.63
The beads can be used repeatedly. They have not yet been
tried on other metal ions.
More selective chelating agents will help improve sepa-
rations of metal ions from each other and from waste
streams. These could aid the recovery of metals from min-
ing wastes and, thereby, reduce the presence of metal ions
in the wrong places. For example, they may help separate
the metal ions obtained by heap leaching of tailings, as done
with sulfuric acid on copper ores. IBC Advanced Tech-
nologies, of Provo, Utah, has attached macrocyclic ligands
of the crown ether type to silica and titania with a spacer to
produce “Super Lig”.64 These can separate lead from tin and
zinc, mercury from sulfuric acid solutions, and lead from
water. They are useful with trace amounts of metal ions and
can be used over again. One such macrocyclic tetracar-
boxylic acid (4.1) selects lead over zinc by a factor of 10.6
(These metals are often found together in ores.)65
Nickel and cobalt also occur together in ores. A new
separation uses a mixture of trioctyl and tridecylamines in
72 Chapter 4

4.1

kerosene in the pores of microporous poly(tetrafluoroethy-

lene).66 Cobalt and copper ions pass through the mem-
brane, but nickel ions do not. A long-sought goal of
chemists is to find chelating agents that are specific for
each metal ion. Progress is being made toward this goal.
Tsukube and co-workers have a ligand (4.2) that is “per-
fectly” selective for silver ion over lead, copper, cobalt, 4.3
zinc, and nickel ions.67
A cross-linked polystyrene polymer (4.3) containing
thiacrown ether groups is able to remove over 99% of
Hg( II ) from dilute aqueous solutions in 30 min, selec-
tively, in the presence of other metal ions.68
A mercaptopropyl nanoporous silica extracts Hg(II) but
not Cd( II ), Pb( II ), Zn( II ), Co( II ), Fe( III ), Cu( II ), or
Ni(II).69 The pore size may play a role in the selectivity.
A calixarene dithiocarbamate (4.4) can separate mer-
cury and gold in the presence of lead, cadmium, nickel, and
platinum.70
Another calixarene, with long alkyl side chains and
eight phosphate groups, has been used to recover uranium
from seawater in 68–94% yields.71 Seawater contains 3
ppb of uranium. The resin could be recycled several times.

III. BIOCIDES 4.4

Biocides are used to prevent organisms from growing in

unwanted places.72 They help keep algae out of swimming
pools and cooling water. They prevent the growth of bacte-
ria and fungi in paints, paper mills, leather factories, and
such. As more and more solvent-based systems are re-
placed by waterborne ones, their use will increase. They are
also used to preserve wood and to keep fouling organisms
off of ships. The use of organomercury compounds in seed
treatments, latex paints, and paper mills has been outlawed.
Pentachlorophenol is no longer used to preserve wood. The
chromium copper arsenate that is used on wood is not en-
tirely free of problems. A study of decks in Connecticut
found that soil beneath the decks contained levels of ar-
senic that exceeded regulatory limits.73 The amount of
chromium approached levels of concern, but were within
regulatory limits. Wood has also been preserved by chem-
ical reaction with carboxylic acid anhydrides, isocyanates,

4.2
Toxic Heavy Metal Ions
4.5
4.6
epoxides, formaldehyde, and acrylonitrile.74 (The last two
are carcinogens.) Supercritical fluids (described in Chap.
8) can be used to help insert these reagents into the wood.
Biocides that release formaldehyde, a known carcino-
gen, are also of some concern. These are often hydrox-
ymethylamines or their ethers, such as (4.5).
N-Chloro compounds, such as 4.6 and 4.7, are also be-
ing looked at as part of the reexamination of the general use
of chlorine compounds. Isothiazolinones, such as 4.8 are
still acceptable. Quaternary ammonium salts, undecylenic
acid, and sorbic acid are also acceptable. The last is used in
the preservation of foods. Sodium and zinc salts of pyri-
dine-2-thiol-N-oxide are also used in personal care prod-
ucts, architectural coatings, and antifoulant paints.55e
Chlorine is often used to inhibit growth of organisms in
cooling water.75 The problem is that it can still kill after it
is put back into the river. (See Chap. 3 for ways of steriliz-
4.7
4.8
73
4.9
ing water.) Chlorine dioxide can be used as a biocide for
process water.76 Ozone treatment is certified for use in
cooling tower water in California.77 A combination of low-
toxicity hydrogen peroxide and peracetic acid controlled
microbial slime in a paper mill for a year at a reduced
cost.78 Tetrakis(hydroxymethyl)phosphonium sulfate
([(HOCH2)4P]2 SO42 ) is suitable for industrial water
treatment.79 It does not bioaccumulate and has nontoxic
degradation products. The typical dose is lower than the
lethal concentration for fish. When air-cooled heat ex-
changers are used, no chemicals are needed and no aquatic
organisms are lost.80
Didecyldimethylammonium chloride is used to prevent
stain and mildew on freshly cut lumber.81 If a quaternary
ammonium salt monomer could be impregnated into wood,
then graft polymerized to it, the process might displace
some of the chromium copper arsenate treatments. Some
antibacterial polymers (e.g., 4.9) work by gradual hydroly-
sis to release the active group.82
Another polymeric biocide (4.10) has been found to ad-
here to cotton to give a “durable” antiodor finish to socks
and towels.83 Poly(hexamethylenebiguanide hydro-
choride) is already used in swimming pools and in personal
care products.
Antifoulant coatings for ships work by the slow leach-
ing of the toxicant into the water. Copper oxide is used, as
well as longer-lasting tributyltin compounds.84 When the
ships are in the deep ocean, the tin compound does not
cause a problem. However, if they are in port most of the
time, as recreational boats are, the metal compounds can
kill desirable animals in the harbor. For example, elevated
4.10
74
4.11
levels of tributyltin compounds have been found in
stranded bottlenose dolphins.85 The International Maritime
Organization has agreed to ban the use of tributyltin com-
pounds in antifouling paints on ships by 2003.86 Thus, it is
desirable to replace them with a system that is more envi-
ronmentally friendly. Rohm and Haas has provided an
isothiazolone (4.11) that can last for 3 years.87 The second
compound, the methacrylate monomer (4.12), is said to
lead to polymers with antifoulant activity.88
An alternative to shedding antifoulant coatings would
be a nontoxic surface to which marine organisms could not
attach, or at least not attach tightly. Silicones and fluo-
ropolymers have been suggested for this purpose.89 The
fluoropolymers include polyurethanes based on fluoroether
polyols and those made from fluorinated acrylates and
methacrylates. Ideally, the motion of the ship through the
water would dislodge the fouling organisms. If not, then
gentle rubbing with brushes or scrubbing with jets of water
could be used. The relatively high cost of the coating would
be offset by the reduced need to repaint.
Many sessile animals in the sea are not fouled by the al-
gae, hydroids, mussels, and barnacles that foul ships, cool-
ing systems of power plants, and aquaculture cages. Nu-
merous investigators are studying the chemical defenses of
sponges, nudibranchs, gorgonians, and bryozoans that re-
pel the usual fouling organisms. Many compounds with an-
tifouling activity have been isolated, including isoni-
triles,90 a pyridine nitro compound,91 brominated
pyrroles,92 and a brominated formamide93, two of which
are shown (4.13 and 4.14). It is hoped that simpler ana-
logues that are more amenable to total synthesis will also
prove to be effective. More needs to be known about the
modes of action of these inhibitors. They may work by
more than one mechanism. Bacteria (such as Pseudomonas
aeruginosa94) settle first on a clean surface and release an
4.12
Chapter 4
4.13
4.14
attractant for the larger fouling organisms. Do the natural
antifoulants inhibit bacterial growth or prevent release of
the attractant or repel the bacteria? Do they inhibit the cur-
ing of the adhesive secreted by the fouling organism? Do
they act similar to insect antifeedants and repel the fouling
organisms? Would insect antifeedants have any effect on
barnacle larvae? The ideal coating would be one that did
not release anything, at least not until triggered by the bac-
teria or the fouling organism. It is possible that a polymeric
coating containing quaternary ammonium salt groups (on
spacers), in an amount such that the coating would swell
somewhat, but not dissolve in seawater, would kill off bac-
teria that tried to grow on the ship.
Efforts are also underway to replace the tin compounds
used as stabalizers in polyvinyl chloride95 and in free radi-
cal reactions in organic chemistry.96
IV. CATALYSTS FOR REACTIONS OTHER
THAN OXIDATION
The search is on for catalysts to replace those containing
toxic heavy metals. The addition of hydrogen chloride to
acetylene to form vinyl chloride is catalyzed by mercuric
chloride. Rhodium (III) chloride on activated carbon works
just as well and is much less toxic.97 It should be tried also
in other addition reactions of acetylene as well as in trans-
esterification reactions of vinyl acetate. The reduction of 2-
ethyl-2-hexenal to 2-ethylhexanol can be catalyzed by a
mixture of copper, zinc, manganese, and aluminum oxides
in 100% yield.98 This is said to be a replacement for car-
cinogenic copper chromite. In Reaction 4.15, the amount of
toxic chromium(II) chloride has been reduced from stoi-
chiometric to catalytic (9–15 mol% chromium(II) chloride)
by the addition of manganese metal.99
Spent catalysts need to be reclaimed either on site or at
a central-processing facility, rather than being sent to a
Toxic Heavy Metal Ions 75

4.15

landfill. However, with metals that are not too toxic, it is

often cheaper to recycle them to other uses.100 Spent nickel
catalysts end up in stainless steel. Others, such as those
containing copper, iron, magnesium, manganese, and zinc,
can be treated with sulfuric acid and then used as micronu-
trients in fertilizer. Several thousand tons of spent catalysts
are recycled this way each year.

V. DYES AND PIGMENTS

Chromium is important in mordant dyeing. Cadmium,

chromium, copper, lead, and mercury have been important
in inorganic pigments. These pigments provide good heat
and light stability at relatively low cost. However, their
manufacture can lead to release of toxic heavy metal ions 4.16
into the environment. Other releases can occur when prod-
ucts made from them end up for disposal in an incinerator
or landfill. Many efforts are underway to replace them with
less harmful materials.
Red cerium sulfide is being developed by Rhone–
Poulenc as a replacement for pigments based on cadmium
and lead.101 Lead chromate is being replaced by nontoxic
yellow bismuth vanadate, which has good hiding power
and lightfastness.102 More expensive organic pigments103
are being used to replace oranges and reds. Many cheaper 4.17
azo pigments lack the light stability needed for outdoor ap-
plications. Two light-stable types made by Ciba-Speciali-
ties, diketopyrrolopyrroles (4.16) and quinacridones (4.17)
are shown.104 White basic lead carbonate has been replaced that it consists of indigo in a clay lattice that contains metal
by titanium dioxide in house paints. Red lead and yellow and metal oxide nanoparticles.107 This suggests the inter-
lead chromate are being phased out of paints. calation of other dyes into clay lattices to produce stable
Bird feathers are often brightly colored, but most con- pigments.
tain no pigments. The colors are due to interference pat- Sewekow has outlined the requirements for eco-textiles
terns. This same principle is now being used in luster pig- for “green garments.”108 These include avoidance of harm-
ments.105 Chemical vapor deposition, sputtering, vacuum ful metals, formaldehyde-containing reagents, halogenated
deposition, as well as aqueous means, are being used to put dye carriers (such as trichlorobenzene), and carcinogenic
thin layers of iron oxide, titanium dioxide, tin oxide, zirco- dyes (such as those based on benzidine and those azo dyes
nium oxide, and others on to mica, aluminum flakes, and that could lead to carcinogenic aromatic amines on reduc-
such, to produce these colors. Thin films of brilliant blue tion). There is already a ban in Germany on azo dyes that
boron nitride have been deposited on silicon by the tita- could release o-toluidine, 2-naphthylamine, and p-
nium( IV ) chloride-catalyzed decomposition of bo- chloroaniline on reduction.109 Most (70%) wool is dyed
razine.106 Investigation of an ancient Mayan blue paint, with chromium mordant dyes. A chromium(III) salt of sul-
which is resistant to acid, alkali, solvents, oxidation and re- fosalicylic acid has been used to avoid the usual after-
ducing agents, biocorrosion, and moderate heat, has shown chrome dyeing with dichromate ion.110 This left 8–15 ppm
76
4.18
chromium(III) in the dyebath, but no chromium(VI). The
dichromate method leaves 13–19 ppm of carcinogenic
chromium(VI). Another worker feels that dyeing with
chromium(III) still has some problems, such as color dif-
ferences between dyeings.111 Iron has been used as a non-
toxic replacement for chromium and cobalt to produce yel-
low, orange, red, blue, brown, and black dyes on protein
and polyamide fibers.112 Disperse dyes have also been ap-
plied to cotton and wool in supercritical carbon dioxide, af-
ter a pretreatment with a polyether, to give light shades.113
This nontoxic, nonexplosive method reduces the amount of
wastewater. Transfer printing done by the sublimation of
dyes from paper to polyester fabrics also reduces the
amount of wastewater. Exhausted dye baths can sometimes
be used for the next batch by the addition of fresh reagents
to reduce the volume of wastewater. The sodium dithionite
and other reducing agents often used to solubilize dyes for
application to fabrics, after which they are insolubilized by
reoxidation, can be replaced by electrolytic reduction.114
This clean use of electricity eliminates waste salts.
Permanent-press fabrics are often cured with N-methy-
lol compounds, such as 4.18, and tend to release formalde-
hyde after the cure. (Formaldehyde [a carcinogen] from
various formaldehyde resins is a problem in some
homes.115) These can be replaced with polycarboxylic
acids, such as the 1,2,3,4-butanetetracarboxylic acid (4.19),
which cure via the cyclic anhydride.116 Both dyeing and
durable-press treatments can be combined in a single step,
if desired.117
No formaldehyde is used in the process, so that none is
released. Copolymers of maleic anhydride should also be
useful in this application and might be cheaper than the
tetracarboxylic acid.305
After exposure, photographic film based on silver chlo-
ride must be processed by a wet process that uses hydro-
4.19
Chapter 4
quinone. For uses such as medical radiography, printing,
industrial radiography, and military reconnaissance, a pho-
tothermographic film can be imaged by a laser, then heated
on a hot roll at 250°F for 15 s, to develop a picture. This in-
volves no wet chemistry and eliminates any effluent.118
Digital cameras, which use no silver, are now available, but
they are more expensive than a regular camera and the pic-
ture quality is not as good.119 Further research is needed to
improve them.
VI. ELECTRICAL USES
Mercury is often used in electrical switches. A nontoxic,
cost-effective drop-in replacement is a gallium alloy con-
taining indium, zinc, and copper.120 The use of mercury
switches is decreasing owing to a shift to solid-state de-
vices.121 Mercury switch thermostats are being replaced by
fully electronic devices. There is still some mercury in ev-
ery fluorescent lamp. There are other ways of generating
light that approximates sunlight. Xenon gas discharge
lamps122 are used in accelerated testing of plastics because
their output is similar to sunlight. They contain no mercury
or other metals. If they can be fabricated to the size needed
in domestic lighting and can operate as efficiently as a flu-
orescent tube, they could provide an alternative to the use
of mercury. If only concentrated light can be obtained from
current xenon lamps, then this might be distributed
throughout the building through optical fibers. One fluo-
rescent lamp uses xenon and a Eu(III)-doped LiGdF4 phos-
phor to produce orange or red light without the need for
mercury.123 Additional phosphors are being studied in an
effort to obtain white light. White light has been produced
by the use of carbon-doped silica as a phosphor.124 This
avoids the need for the use of metals, such as silver, cad-
mium, germanium, and rare earths, that are present in the
usual phosphor in a fluorescent lamp. No mercury is used.
A GaN light-emitting diode with a “white” phosphor has
been suggested for lighting.125
There is a controversy over the use of electric cars pow-
ered by lead-acid batteries. One group claims that this will
increase the amount of lead entering the environment
greatly for a marginal amount of ozone reduction.126 Oth-
ers claim that this analysis is faulty127 and that lead in the
environment would not increase that much. The tetraethyl-
lead formerly used as an antiknock agent in gasoline was a
major source of lead in the environment. It has been re-
placed by tert-butylmethyl ether, ethanol, and aromatic hy-
drocarbons as antiknock agents. There is an effort to use
methylcyclopentadienylmanganese tricarbonyl for this
purpose in the United States, which is controversial.128
Ethyl Corp. feels that the compound is harmless, for it has
been used in Canada for 19 years. Critics say no systematic
Toxic Heavy Metal Ions 77

study has been done to measure its effects in Canada. Auto

makers say that it interferes with catalytic converters and
sensors in cars. The alternatives mentioned in the foregoing
contain no metal.
There is a problem with the widespread use of arsenic,
cadmium, and selenium in electronic and photovoltaic de-
vices. Cadmium mercury telluride is used in infrared-sens-
ing night goggles. Cadmium sulfide, cadmium selenide,
gallium arsenide, and analogues, are used in solar cells. If 4.20
their use becomes widespread, then an efficient system of
collecting used cells for reprocessing will be needed. Some
workers feel that it will be better to use nontoxic silicon
ion-exchange resin.140 In another, the chromium(III) is ox-
cells wherever possible. (Solar cells are discussed in Chap.
idized to chromium(VI), then taken through a cation-ex-
15.)
change resin to remove sodium ion, reduced back to
The preparation of gallium arsenide is a dangerous pro-
chromium( III ), and finally collected on another ion-ex-
cess employing two pyrophoric reagents (4.3):129
change resin.141 Chromium( III ) has also been recovered
Ga(CH3)3  AsH3 → GaAs  3 CH4 (4.3) on activated carbon at pH 5.142 Chromium-free collagen
130 has been obtained from leather waste, and the chromium
Chemical vapor deposition of a single source precursor
has been recycled.143 Leather buffing dust has been tested
offers a safer alternative (4.4):131
as a filler for rubber.144 Leather shavings and scraps from
Ga(As(tert-butyl)2)3 → GaAs (4.4) shoe parts can be impregnated with synthetic polymers for
molding into useful objects, or molded alone under heat
Gallium nitride can be prepared by the pyrolysis of gallium
and pressure.145
dialkylamides. Wherever possible, it would be safer to sub-
Iron, titanium, and zirconium salts can be substituted
stitute gallium nitride for gallium arsenide. Cadmium se-
for the chromium ones.146 Vegetable tannins, such as 4.20
lenide can be made by the pyrolysis of cadmium 2-pyridi-
can also be used, but they slow down the tanning process.
neselenolate.132 Thin films of cadmium telluride have been
Similar phenols can be found in the residue from tea leaves
made by spraying a mixture of cadmium and tellurium
left after the manufacture of instant tea. Perhaps, they
compounds dissolved in a trialkylphosphine on to a sub-
could be used in making leather to eliminate or reduce the
strate at temperatures higher than 250°C.133 Cadmium
amount of another waste product. Getting reagents to pen-
phosphide can be made by pyrolysis of a cadmium phos-
etrate the hide is a problem. Newer methods, such as ul-
phine complex.134 Such methods are described as less toxic
trasonication and supercritical fluid extraction, may help
and easier to control. They avoid the use of the toxic gases
reduce the time required to make leather, so that these
hydrogen selenide and telluride.
alternative-tanning agents can be used instead of the
chromium.
VII. LEATHER

Most leather is tanned with chromium(III) salts, which re-
act with carboxyl groups in the collagen, so that it is no
longer biodegradable.135 A ton of raw hide produces 200
kg of good leather.136 Untanned rejects end up as gelatin
and glue. In a typical case, only 60% of the chromium is
taken up by the leather, the rest are discharged in waste
liquors.137 Silvestre and co-workers claim to have opti-
mized the process to obtain complete removal of the
chromium from a bath of water and tetrachloroethylene.138
This eliminates a pollution problem with chromium, but in-
troduces an undesirable solvent. If the hide is pretanned
with glutaraldehyde, the chromium usage can be reduced
by 50%.139 Various schemes have been devised to recover
the chromium from the wastewater for reuse. In one, more
than 98% of the chromium is recovered with a carboxylic
VIII. METAL FINISHING
Electroplating wastes have often contaminated waterways.
A number of nonaqueous methods are available that avoid
this problem. These include dipping (as in galvanizing steel
with zinc), cladding, laser-assisted coatings, thermal spray
coatings, vacuum metallization, chemical vapor deposi-
tion, sputtering, and in-mold metallization of plastics.147
Sol–gel ceramic coatings are also used. Work has also been
done at Los Alamos on laser-driven vapor deposition to de-
posit uniform coatings.148 Recent work has been summa-
rized in a U.S. Environmental Protection Agency guide to
alternative metal finishes, from which much of the follow-
ing discussion has been taken.149 The EPA has also set up
a National Metal Finishing Center at Ann Arbor, Michi-
78
gan.150 The coatings are designed to prevent corrosion, in-
crease wear, and to improve the appearance of objects.
Cadmium coatings impart corrosion resistance and nat-
ural lubricity. They are usually applied from an electro-
plating bath of cadmium cyanide. Wastewater from this
process must be treated to remove both toxic ions. Other
anions such as fluoroborate, sulfate, chloride, and py-
rophosphate can sometimes replace cyanide. Zinc–nickel,
zinc–cobalt, and zinc–tin alloys can be plated as replace-
ments for cadmium. They have the necessary corrosion and
wear resistance, but not the lubricity of cadmium coatings.
Aluminum deposited by ion vapor deposition can replace
cadmium coatings in some applications. In this process,
there are no toxic materials and no liquid waste. The pro-
cess involves evaporating aluminum and partially charging
it in a vacuum before it is deposited on a substrate of the op-
posite charge. Such coatings may require the use of a lu-
bricant to replace the natural lubricity of cadmium. They
can be porous, in which case, they may have to be peened
(rubbed) with glass beads to eliminate the pores.
The use of chromium plating for decorative effects is
subject to the whims of fashion. Twenty years ago, each car
had chromium-plated bumpers and strips. Today, very few
do. Plastic wheel covers are still shiny from what are prob-
ably aluminum coatings. Where the wear resistance of
chromium coatings is important, as in machine parts, a
coating of hard titanium nitride can be applied by physical
vapor deposition. (Coatings of silicon dioxide and alu-
minum oxide can also be applied by vapor deposition.) The
electroplating of nickel–tungsten–silicon carbide and
nickel–tungsten–boron alloys is also being studied as a
substitute for chromium coatings. Chromate is also used
for conversion coatings for aluminum and zinc. The coat-
ings provide corrosion resistance and may help adhesion of
organic coatings. Zirconium deposited on the surface as
zirconium oxide can substitute for the chromate. Titanates
and molybdates have also been studied for this application.
The etching of polyvinyl chloride surfaces before plating
can be done with ultrasound instead of the CrO3/H2SO4
that is often used.151
Cyanide is no longer needed in the electroplating of cop-
per. There are commercially available alternatives. The
formaldehyde used in the electroless deposition of copper
coatings is carcinogenic. A nonhazardous reductant is
4.21
Chapter 4
needed to replace the formaldehyde. These methods still
require treatment of the wastewater to remove copper ion.
A new method is available that replaces silver in the sil-
vering of mirrors.152 A reflective multilayer coating of sil-
icon and silica deposited by chemical vapor deposition re-
places the usual metal films.
IX. OXIDATION
A. Introduction
Organic chemists often use stoichiometric amounts of
heavy metal compounds as oxidants. These reagents in-
clude chromium oxides, potassium dichromate, pyridinium
chlorochromate, potassium ferricyanide, lead dioxide, lead
tetraacetate, manganese dioxide, manganese( III ) acetate,
potassium permanganate, mercuric oxide. osmium tetrox-
ide, silver oxide, and others. These result in large amounts
of waste that must be disposed of or recycled. Traces of
them may remain in the wastewater or the product. Many
of these contain metal compounds that are quite toxic. The
activation of CMH bonds with reagents, such mercuric ac-
etate and selenium dioxide, has these problems. Even
reagents, such as sodium hypochlorite and m-chloroperox-
ybenzoic acid, result in much waste, although it is much
less toxic.
Schemes have been devised to substitute less toxic met-
als for more toxic ones. Potassium ferrate on K10 mont-
morillonite clay has been used to replace potassium chro-
mate and potassium permanganate in the oxidation of
alcohols to aldehydes and ketones in 54–100% yields.153
The potassium ferrate is made by the action of sodium
hypochlorite on iron( III ) nitrate or by treatment of
iron(III) sulfate with potassium peroxymonosulfate.154 Af-
ter the oxidation, any excess oxidizing agent, and its re-
duced form, are easy to recover by filtration or centrifuga-
tion. In another case, manganese-containing reagents have
been substituted for more toxic ones containing chromium
and selenium (4.21).155 Selenium dioxide was used for-
merly in the first step and pyridinium chlorochromate in
the second.
This process still generates large amounts of waste.
Oxidizing reagents have also been immobilized on ion-
Toxic Heavy Metal Ions
4.22
exchange resins for ease of separation.156 The base poly-
mer was a crosslinked poly(methyl methacrylate) (4.22).
This reagent was used to oxidize alcohols to aldehydes and
ketones in 80–88% yields. The reagent could be regener-
ated for reuse by extracting the manganese with ferrous
ammonium sulfate, then treating with permanganate ion.
“Magtrieve,” based on chromium dioxide, is marketed as a
magnetically retrievable oxidant for conversion of benzylic
or allylic alcohols to aldehydes in 75–90% yields.157 The
by-product trivalent chromium oxyhydroxide stays on the
magnetic crystal surface for easy retrieval. The solid can be
reconverted to the active form by heating in air. (The use of
other supported reagents is described in Chap. 5.)
The trend is toward oxidants that are relatively harmless
and that generate no noxious by-products. Oxygen, and
materials derived from it, are examples. Ozone is quite
toxic itself, but produces no harmful by-products. It is used
commercially for the cleavage of oleic acid to azelaic and
pelargonic acids.158 Hydrogen peroxide is made from oxy-
gen (4.23).159
The anthraquinone is reduced back to the anthrahydro-
quinone with hydrogen using a nickel or palladium catalyst
to complete the cycle. The anthraquinone used may also
contain a 2-ethyl group. Efforts to prepare cheaper hydro-
gen peroxide by direct reaction of hydrogen and oxygen
over palladium and platinum catalysts have been hampered
by low yields and selectivity,160 although significant im-
provements have been claimed.161 In most cases, too much
water is produced at the same time. Nagashima et al. ob-
tained 98% selectivity to produce 1.33% aqueous solutions
of hydrogen peroxide. A 13% aqueous solution of hydro-
gen peroxide was obtained in 97% selectivity using a 20:1
Pd/Pt catalyst.162 If an inexpensive way can be found to
4.23
79
concentrate these solutions to 30%, these could become
commercial processes. Perhaps a zeolite membrane, (e.g.,
from a 3-A molecular sieve), can be found for this separa-
tion. Generation of the hydrogen in situ from water and car-
bon monoxide has also been used to make hydrogen
peroxide.163
Several other oxidizing agents can be made from hydro-
gen peroxide and thus be derived indirectly from oxygen.
These include sodium perborate, sodium percarbonate,
urea peroxide, peracids, potassium peroxymonosulfate,
amine oxides, dioxiranes, and iodosobenzene (4.24).
Oxygen and many of these derived oxidizing agents are
used with transition metal catalysts, which must be recov-
ered and recycled. A typical mechanism is 4.5:
RH  Co(III) → R  Co(II)  H
R  O2 → ROO → ROOH  R
RH
(4.5)
ROOH  Co(II) → RO  Co(III)  OH
RO  RH → ROH  R
The ligands on these metal ions often tend to be oxidized at
the same time as the substrate, leading to low turnover
numbers.164 Efforts to stabilize porphyrin ligands have in-
volved replacement of the most oxidizable hydrogen atoms
on the pyrrole rings with halogen atoms and putting halo-
genated aryl groups in the meso-positions.165
Oxidation of ligands can be avoided by the use of purely
inorganic catalysts. If the catalysts are insoluble in the
medium, as in zeolites or heteropolyacids, the workup is
much simpler. If the oxidation can be run in the gas phase
or in a melt, no solvent has to be separated. If the oxidant is
oxygen, a membrane reactor can sometimes be used to
keep the oxygen concentration low and allow the product
to be separated continuously, thereby avoiding
overoxidation.
There are many reviews that cover various aspects of
oxidation. These include ones on alkane activation,166 cat-
alytic selective oxidation,167 metal complexes of dioxy-
gen,168 metal-catalyzed oxidation,169 biomimetic oxida-
tions,170 oxidation with peroxides,171 catalytic oxidations
with peroxides,172 catalytic oxidations with oxygen,173 ox-
idations with dioxiranes,174 and oxidation of pollutants.175
80
4.24
Recent techniques of reducing metal ion pollution by these
methods are described in the following sections.
B. Oxidation by Oxygen
Although oxidations by oxygen are not common in the
usual laboratory and in the manufacture of fine chemicals,
they are often the standard methods of making large-vol-
ume commodity chemicals. Some typical ones are given in
reactions 4.25–4.32.176
m-Xylene can be oxidized to isophthalic acid by the
method used to make terephthalic acid (4.25). Nylon plants
that make adipic acid sometimes lose polluting nitrogen
4.25
4.26
Chapter 4
oxides (4.29). The synthesis of acetaldehyde from ethylene
(4.29) employs a tandem oxidation in which the copper(II)
chloride reoxidizes the palladium(O) and oxygen reoxi-
dizes the copper(I) chloride formed in the process. A sim-
ilar synthesis has been used to convert 1-decene to 2-de-
canone. Polyaniline was used with palladium( II ),
eliminating the need for copper(II) chloride and the corro-
sion caused by chloride ion.177 The vanadium pyrophos-
phate (4.32) used in the oxidation of butane to maleic an-
hydride is encapsulated in silica to strengthen it for use in a
recirculating fluidized solids reactor.178 The use of tert-
butylhydroperoxide to convert propylene to propylene ox-
ide produces the valuable by-product isobutylene, which
can be converted to tert-butylmethyl ether, an antiknock
agent for gasoline. If ethylbenzene is used instead of isobu-
tane, the by-product is styrene, which can be polymerized
to polystyrene. The only defect in such syntheses is that the
market demand must be large enough to absorb all of the
by-product. Such syntheses eliminate not only the waste
salts, but also the toxic chlorine used in the hypochlorous
route to propylene oxide (4.33).
Epoxides can also be made by direct oxidation by oxy-
Toxic Heavy Metal Ions 81

4.27

4.28

4.29

4.30

4.31

4.32

4.33
82
4.34
gen (4.34). Propylene can be oxidized by air using a ruthe-
nium porphyrin catalyst, but the reaction is slow.179 An-
other technique that produces a useful by-product involves
the cooxidation of an aldehyde, the reaction probably in-
volving a peracid intermediate. Two examples illustrate not
only this point but also the use of heterogeneous catalysts
for ease of separation of the product. This also avoids loss
of the metal-containing catalyst and facilitates its reuse. In
the first, -pinene is converted to its epoxide with a mag-
nesium oxide supported polytitazine cobalt complex. The
catalyst is made from magnesium oxide, titanium tetra-
chloride, ammonia, and cobalt(II) chloride hexahydrate.180
The by-product isobutyric acid might be dehydrogenated to
methacrylic acid. (In other examples in the literature, ac-
etaldehyde has been used as the aldehyde, leading to acetic
acid as the byproduct.) Isobutyraldehyde has also been
used in the conversion of olefins to their epoxides by oxi-
dation with oxygen in the presence of a cobalt(II) catalyst
supported on silica or polyaniline.181 The catalyst on silica
is made by reacting hydroxyl groups on the surface of sil-
ica with 2-cyanoethyltriethoxysilane, followed by hydroly-
sis of the nitrile to the carboxylic acid and its conversion to
the cobalt salt with cobalt(II) acetate (4.35). Cyclohexene
was converted to its epoxide (85% conversion) with no
other alkene-derived products being formed. The catalyst
was reusable. (See Chap. 5 for more detail on supported
catalysts.)
Chromates and permanganates are often used in the ox-
idation of alcohols to aldehydes, ketones, and carboxylic
4.35
Chapter 4
acids. These transformations can also be carried out with
oxygen, in at least some cases. A copper phenanthroline–
calcium hydroxide catalyst was used with oxygen to con-
vert primary alcohols to the corresponding aldehydes in
95% selectivity at low conversions, but only 75–80% se-
lectivity at higher conversions. Secondary alcohols were
converted to the corresponding ketones with 100% selec-
tivity.182 Oxygen has been used with a palladium(II)
acetate catalyst to oxidize 1-octadecanol to the correspond-
ing aldehyde in 95% yield at 96% conversion and 2-de-
canol to the corresponding ketone in 98% yield at 97% con-
version.183 A molybdovanadophosphate on charcoal
catalyst was used with oxygen for reactions 4.36.184 An
iron vanadate catalyst was used with oxygen to convert flu-
orene to fluorenone in 60% yield (4.37). However, if this
catalyst was doped with cesium ion the yield rose to over
95%.185
Glucose can be oxidized to gluconic acid by oxygen
(4.38) in the presence of palladium on alumina, a palla-
dium–bismuth catalyst, or a platinum–bismuth catalyst in
99–100% yield.186
Gluconic acid is a possible substitute for the sodium
tripolyphosphate used in detergents to complex calcium
and magnesium ions in the water. The phosphate can cause
algal blooms in rivers and lakes receiving the wastewater
from the washing process. This method can also be used for
further conversion of the gluconic acid to 2-ketogluconic
acid with 98% selectivity at 98% conversion.187 Such
methods are also applicable to a variety of related carbohy-
drates and other alcohols.188 Glycerol may be in surplus if
Toxic Heavy Metal Ions 83

4.36

2,3-dihydroxypropionate to 2-hydroxymalonic acid with

4.37
4.38
the conversion of oils to methyl or ethyl esters for biodiesel
fuel becomes common. It has been converted to glyceric
acid in 70% yield using the foregoing method of air oxida-
tion.189 The method has also been used to convert calcium
80% selectivity at 90% conversion.190 The method allows
the conversion of the hydroxyl group in 10-undecen-1-ol to
a carboxylic acid without touching the double bond.191
Ethylene glycol can be oxidized to glycolic acid in 80–94%
conversion and 90–100% selectivity using a gold-on-car-
bon catalyst with oxygen.192 This catalyst deactivates more
slowly than Pd/C and Pt/C ones.
One molar aqueous ethylene glycol has been converted
to glycolaldehyde in 90% yield using an alcohol oxidase, a
method said to give better selectivity than chemical meth-
ods.193 Laccase has been used with oxygen in the presence
of an azine to convert benzyl alcohols to aldehydes in
87–100% yields.194 (For more on biocatalysis, see
Chap. 9.)
Two reactions illustrate the use of air oxidation where
toxic selenium dioxide or bromination followed by hy-
drolysis and oxidation would normally be used. The first
(4.39) oxidizes a methylphenol to a phenolaldehyde in
95% yield.195 The second (4.40) uses air to oxidize -
pinene to verbenone in 77% yield.196 This eliminates the
need for the lead tetraacetate, sodium dichromate, sulfuric

4.39

4.40
84
4.41
4.42
acid, and benzene in the two step procedure in Organic
Syntheses.197
Use of a heterogeneous catalyst simplifies workup. A
copper-modified hydrotalcite was used to catalyze the oxi-
dation of phenylacetylene by oxygen (4.41), giving yields
comparable with those obtained in homogenous oxida-
tions.198
Binaphthols are important as ligands for transition metal
catalysts used in stereoselective syntheses. The oxidation of
a suspension of powdered 2-naphthol in water with ferric
chloride and air gives the corresponding binaphthol (4.42)
in 95% yield. This is an improvement over homogeneous
syntheses which are accompanied by quinone formation.199
The workup consists of filtration, washing with water, dry-
ing, and recrystallization from toluene. The reaction can
also be run with a catalytic amount of inexpensive cop-
per(II) sulfate on alumina to produce the binaphthol in 97%
yield.200 A third paper reports 77–99% yields with 1 mol%
of a tetramethylethylenediamine complex of copper hy-
droxychloride as the catalyst.201
Efforts are being made to overcome some of the failings
of the present syntheses of commodity chemicals. Most
phenol is produced by the acid-catalyzed cleavage of
cumene hydroperoxide. The by-product is acetone. The
4.44
Chapter 4
problem is that the market demand for the two is not always
equal. Many attempts are being made to oxidize benzene (a
carcinogen) directly to phenol. In one, hydrogen peroxide
is generated in situ in the presence of a palladium/copper
on silica catalyst (4.43). Although this gives phenol with
90% selectivity, the rate is slow and too much water is pro-
duced.202
Pd-Cu on silica
C6H6 
 
H2,O2
→ C6H5OH  H2O
4.43
(Solutia is building a plant that will use waste N2O to ox-
idize benzene to phenol with almost 100% selectivity using
an FeZSM-5 [a zeolite] catalyst. The phenol will be hydro-
genated to cyclohexanone.203) Adipic acid for nylon is usu-
ally made by oxidation of cyclohexane with oxygen to a
mixture of cyclohexanone and cyclohexanol, which is then
converted to adipic acid by nitric acid (4.44). Some of the
by-product nitrogen oxides escape causing air pollution. A
heteropolyacid containing phosphorus, molybdenum, and
vanadium can be used with oxygen instead of the nitric acid
to convert 2-methylethyl-hexanone to 6-ketoheptanoic acid
avoiding both the nitrogen oxides and corrosion.204
Toxic Heavy Metal Ions
When this method is applied to cyclohexanone, it pro-
duces a mixture of 50% adipic acid, 19% glutaric acid, and
3% succinic acid. Further work is needed to steer the reac-
tion to a high yield of the desired adipic acid. A chromium
aluminum phosphate molecular sieve has been used with
oxygen and a catalytic amount of a hydroperoxide to con-
vert cyclohexane to a mixture of 48% cyclohexanone, 5%
cyclohexanol, 6% cyclohexanehydroperoxide, and 40%
adipic acid, at 10% conversion. The catalyst could be
reused four times without loss of activity.205 Presumably,
the products other than adipic acid could be recycled to the
next run. The authors do not give the selectivity at higher
conversions. Ideally, one would like a similar system that
would give only adipic acid at 100% conversion.
High selectivity at high conversions has been observed
in the photocatalyzed oxidation of hydrocarbons in zeolites
using oxygen.206 Even red light can be used. In some cases,
dyes are exchanged for the alkali cations of the zeolites.
The yield of one of several possible products from 2-
methylpentene and 1-methylcyclopentane can be as high as
100%, compared with much lower selectivity when the re-
action is run in solution. Scaling-up these processes to a
commercial scale poses significant challenges. Perhaps, a
fluidized bed of powdered zeolite can be used in a tubular
reactor. A solvent-free way to desorb the products from the
zeolites is needed. Perhaps, simple heating will suffice.
(For more on oxidations in zeolites, see Chap. 6.)
Care must be used in all of these oxidations to avoid
fires and explosions. This means operating outside the ex-
plosive limits of the system. It also means testing for per-
oxides before workup. A common method is to see if a
sample liberates iodine from a solution of potassium io-
dide. Chemists at Praxair Inc. have devised a reactor that
uses pure or nearly pure oxygen below a gas containment
baffle with nitrogen above.207 The oxygen efficiency is
about 99%, which allows increased productivity and selec-
tivity at lower-operating pressures or temperatures. The
rate of reaction is increased. The amount of vent gas, lost
solvent, and lost reactant are reduced. In the oxidation of p-
xylene, 25–62% less loss to carbon monoxide and dioxide
was found together with less color.
C. Oxidation with Hydrogen Peroxide Without
Titanium
The problem of nitrogen oxides emissions from nylon
plants was mentioned previously. Mallinckrodt produces
nitrogen oxides when it dissolves metals in nitric acid. By
using hydrogen peroxide to oxidize the nitrogen oxides to
nitric acid, it has eliminated 30 tons/year of the oxides and
reduced its nitric acid use by 109 tons/year.208
85
The need for a process for the direct conversion of ben-
zene to phenol was mentioned in the foregoing. A polymer-
supported vanadyl chelate has been used (at 1 mol%) to ob-
tain phenol (100% selectivity at 30% conversion) by
treatment with 30% hydrogen peroxide.209 There was no
leaching of the metal ion. The catalyst could be recycled
ten times before it started breaking up. Further work with
an inorganic support might allow the development of a
commercial process.
The use of hydrogen peroxide to replace the chlorine
and sodium hypochlorite used to bleach paper and textiles
was discussed in Chap. 3.
Olefins can be converted to the corresponding epox-
ides with hydrogen peroxide under a variety of condi-
tions. The yields were 44–98% in buffered dimethylfor-
mamide.210 Catalysis by a manganese 1,4,7-trimethyl-
1,4,7-triazacyclononane complex gave over 98% yields
with styrene, cis-2-hexene, and 1-hexene with turnover
numbers of 1000, 540, and 270, respectively.211 When
this ligand was used with a manganese-exchanged fauja-
site zeolite, the epoxidation of cyclohexene was 95% se-
lective at 47% conversion.212 (See Chap. 6 for zeolites.) If
ligand destruction can be minimized by choice of a more
durable ligand, this may be a very useful system. When
the manganese was complexed with a tetraarylporphyrin-
carboxylic acid, cyclooctene was oxidized to the corre-
sponding epoxide in 100% yield in 3 min at 0°C.213
Putting a manganese bipyridyl complex into a zeolite
gave a catalyst good for 1000 cycles. In contrast to
many catalysts, it showed no tendency to decompose hy-
drogen peroxide and underwent no self-oxidation.214 By
adjusting the acidity of the zeolite, the temperature, and
time of the reaction, it was possible to favor epoxides, di-
ols, or diacids. After 4 h (22% conversion) at 20°C, the
product consisted of 81% epoxide and 14% diol. After 18
h at the same temperature, cyclohexene (62% conversion)
gave 6% epoxide and 79% diol. At 100% conversion (40
h), the product was the diacid in 80% yield. Repeated re-
generation of the catalyst was possible. This type of cata-
lyst offers considerable promise, especially if the zeolite
cavity can be chosen to favor a given product in higher
selectivity. As a solid, it allows ease of separation from
the mixture and the possibility of use in a column, if the
rate can be increased by the use of higher temperatures. It
might be suitable as a replacement for the more toxic
ozone in the cleavage of oleic acid to nonanoic and aze-
laic acids.
Solid catalysts can offer ease of separation as well as
high selectivity. Cyclohexene has been converted to its
epoxide with hydrogen peroxide and hydrotalcite
(Mg10Al2(OH)24CO3) in methanol at 60°C in more than
86
4.45
99% yield at 100% conversion.215 With 1-octene, the yield
was 95% at 95% conversion. No transition metal is needed.
The high yields may be at least partly due to the presence
of the base, which may prevent the ring-opening side reac-
tions often found in media lacking a base. The catalyst can
be reused with no loss in activity. Solid catalysts with no
organic ligands may last longer, because there is no organic
ligand to be oxidized. Oxidatively and solvolytically stable
manganese-substituted heteropolyanions, such as the Keg-
gin compound [( Mn( II )( H2O)3)2(SbW9O33)2]12, gave
more than 99% regioselectivity in the oxidation of
limonene if a biphasic system of ethylene dichloride–water
was used (4.45).216 However, there was some isomeriza-
tion to the corresponding allylic alcohol during the
reaction.
A “green” route to adipic acid uses no solvent or halide
ion and produces no nitrogen oxides.217 Four equivalents
of 30% aqueous hydrogen peroxide are used with air,
sodium tungstate, and CH3(C8H7)3NHSO4 (as a phase
transfer catalyst) to oxidize cyclohexene to adipic acid in
90–93% yield. After the adipic acid is filtered off, the
aqueous phase can be reused by adding more phase-trans-
fer catalyst and hydrogen peroxide. The reaction probably
proceeds through the epoxide and glycol. For this method
to be used commercially, the price of hydrogen peroxide
must be lower. The method has also been used to oxidize
2-octanol to 2-octanone in 95% yield.218 The aqueous
layer was combined with the residue from distillation of
the ketone for use in the next run. Benzyl alcohols can be
4.46
Chapter 4
converted to the corresponding aldehydes in 82–91%
yields using less than 1.5 equivalents of hydrogen perox-
ide. If 4–5 equivalents of hydrogen peroxide are used, the
corresponding carboxylic acid results in 80–91%
yields.219
If the hydrogen peroxide is used with a catalytic amount
of a ketone, such as hexafluoroacetone, olefins can be con-
verted to epoxides, aldehydes to acids, sulfides to sulfox-
ides, tertiary amines to amine oxides, and so on.220 The ac-
tive reagent is the hydroperoxide resulting from the
addition of hydrogen peroxide to the carbonyl group of the
ketone. Styrene is cleaved to benzaldehyde and formalde-
hyde in 95% yield by hydrogen peroxide in acetic acid us-
ing a vanadyl acetate catalyst. Peracetic acid may be
formed as an intermediate.221 The Baeyer–Villiger oxida-
tion of a ketone to a lactone can also be carried out with hy-
drogen peroxide. A trace of poisonous selenium dioxide is
used in Reaction 4.46.222 The toxicity would be lowered if
the selenium could be attached to a solid support in such a
way that none would leach out. The reaction has also been
run on cyclobutanones to convert them to the correspond-
ing lactones in 90% yield.223 The catalyst, without which
the reaction did not occur, was a heterocyclic quaternary
ammonium salt.
Methylrheniumtrioxide has been used as a catalyst for
the oxidation of methylnaphthalenes, phenols, and phenol
ethers to quinones with hydrogen peroxide (4.47).224 The
product ratio was 7:1 in favor of the desired vitamin. The
current industrial preparation of the vitamin with chromium
trioxide gives 38–60% yields. This results in 18 kg of
chromium-containing waste per 1 kg of vitamin. Hydrogen
peroxide of this concentration is hazardous to use. Water is
an inhibitor for the reaction. However, it is possible to use
35% hydrogen peroxide with acetic anhydride to give a 10:1
selectivity for the desired vitamin. Rhenium oxides also
work, but give lower yields. Further work is needed to find
an active rhenium catalyst that is easy to separate and recy-
cle to the next run. Rhenium compounds are not very toxic.
Methylrheniumtrioxide can also be used with 30% hydro-
gen peroxide to convert olefins to epoxides with more than
Toxic Heavy Metal Ions
4.47
98–99% selectivity.225 A pyridine or bipyridine is used to
accelerate the oxidation and prevent ring opening to by-
products.
Hydrogen peroxide can be used with molybdenum and
tungsten catalysts to provide a convenient source of
bromine in situ from bromide ion.226 This mimics the ac-
tion of haloperoxidase enzymes. It provides a less haz-
ardous way to use bromine. Soybean peroxidase can be
used with hydrogen peroxide to oxidize alcohols to aldehy-
des and ketones.227 The use of hydrogen peroxide with an
immobilized lipase has allowed the oxidation of linoleic
acid to a monoepoxide in 91% yield. The enzyme could be
reused 15 times.228 Indole has been oxidized to oxindole in
95% yield using hydrogen peroxide with a chloroperoxi-
dase (4.48a).229
(Additional oxidations and other reactions catalyzed by
enzymes are described in Chap. 9.)
The hazards of concentrated hydrogen peroxide can be
avoided by using sodium perborate, sodium percarbonate,
4.48a
4.48b
87
and urea peroxide. The first two are inexpensive, stable,
nontoxic, easily handled bleaching agents used in deter-
gents. They are suitable for many types of oxidation, such
as formation of epoxides from olefins, oxidation of sulfides
to sulfoxides, and sulfones, lactones from cyclic ketones,
and so on.230 Sodium perborate has a cyclic structure
(4.48b). The other two are just hydrogen-bonded com-
plexes. The urea hydrogen peroxide complex can be stored
a year at room temperature.231 A few examples of the re-
cent uses of these compounds will be given. Sodium perbo-
rate has been used to regenerate ketones from their oximes
in 80–91% yields,232 to epoxidize ,-unsaturated ketones
in 80–95% yields233 and to generate bromine from sodium
bromide in situ for brominations.234 Salicylaldehyde has
been converted to catechol with sodium percarbonate
(4.49) in 91% yield.235
Urea peroxide has been used with methylrheniumtriox-
ide to epoxidize allylic alcohols236 and to oxidize 2,5-
dimethylfuran to 3-hexene-2,5-dione (97% yield).237 This
88
4.49
avoids the need for the use of concentrated hydrogen per-
oxide with this catalyst. The urea also avoids acid-cat-
alyzed secondary ring-opening reactions through its buffer-
ing action. The urea–hydrogen peroxide complex can also
be used to oxidize secondary amines to nitroxides
(4.50).238
Ethyl phenyl sulfide can be oxidized to the sulfoxide in
97% yield using 30% aqueous hydrogen peroxide in
1,1,1,3,3,3-hexafluoro-2-propanol.239 No sulfone is
formed. The fluorinated alcohol (bp 59°C) is recovered by
distillation for use in the next run.
D. Oxidation by Hydroperoxides Without
Titanium
The commercial process for the production of nylon 6
starts with the oxidation of cyclohexane with oxygen at
160°C to a mixture of cyclohexanol and cyclohexanone
with a cobalt(II) catalyst. The reaction is taken to only 4%
conversion to obtain 85% selectivity. Barton and co-work-
ers have called this the least efficient major industrial
chemical process.240 They have oxidized cyclohexane to
the same products using tert-butylhydroperoxide with an
iron(III) catalyst under air (70°C for 24 h) with 89% effi-
ciency based on the hydroperoxide. The oxidation of cy-
clohexanol to cyclohexanone was carried out in the same
way with 99% efficiency. A cobalt catalyst in MCM-41 ze-
olite gave 38% conversion with 95% selectivity in 4 days
at 70°C.241 These produce tert-butyl alcohol as a coprod-
uct. It can be dehydrated to isobutene, which can be hydro-
4.50
Chapter 4
genated back to isobutane for recycle to the process or re-
acted with methanol to give the antiknock agent for gaso-
line, tert-butylmethylether. This process may be economi-
cal if the time can be reduced. Other workers have used
manganese catalysts for the oxidation of cyclohexane, but
have obtained lower yields.242
One of the commercial processes for the production of
propylene oxide uses the transition metal-catalyzed epoxi-
dation by tert-butylhydroperoxide. Recently, various
molybdenum complexes have been used to catalyze the
epoxidation of other olefins by tert-butylhydroperoxide.
Cyclooctene is converted to its epoxide quantitatively us-
ing a molybdenum complex of N-octadecylpyridylpyra-
zole.243 Cyclohexene has been converted quantitatively to
its epoxide using a polyimidetriazole molybdenum com-
plex.244 The catalyst could be recycled ten times, although
the yield fell to 92% in the sixth cycle and to 70% in the
tenth cycle. Putting the molybdenum complex in a molec-
ular sieve raised the conversion in the epoxidation of
styrene from 25 to 96% (94% selectivity). Thus, both the
rate and yield increased.245 These methods provide ease of
separation of the catalyst from the reaction mixture for
reuse, as well as improved yields. Further work is needed
to keep the yields up with the recycled catalysts. It may be
necessary to use inorganic ligands or supports, rather than
organic ones, to achieve this.
It may not be necessary to use a transition metal catalyst
at all. A 96% yield has been obtained in the epoxidation of
Toxic Heavy Metal Ions
4.51
a cyclic ketone using tert-butylhydroperoxide with a potas-
sium fluoride on a alumina catalyst (4.51).246
When 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was
used as a catalyst in the oxidation of an unsaturated lac-
tone by tert-butylhydroperoxide, the yield was 75%.247
This was the only amine that worked well. These experi-
ments suggest that other strong-base, solid catalysts
should be tested. Silica has been used as an environmen-
tally benign and recyclable catalyst with tert-butylhy-
droperoxide. This system gave an 86% yield of sulfoxide
from a sulfide.248 Another insoluble catalyst, made by ex-
changing the sodium ion in zeolite Y with a copper histi-
dine complex, gave 100% selectivity in the oxidation of
an alcohol to a carboxylic acid using tert-butylhydroper-
oxide.249
Secondary alcohols have been oxidized to ketones with
excess tert-butylhydroperoxide in up to 93–99% yields us-
ing a zirconium catalyst.250 Zirconium catalysts have also
been used with tert-butylhydroperoxide in the oxidation of
aromatic amines to nitro compounds and of phenols to
quinones. Allylic oxidation of steroids in 75–84% yields
has been performed with tert-butylhydroperoxide and cop-
4.52
4.53
89
per halide catalysts, thus avoiding chromium-containing
reagents.251
E. Oxidations by Hydrogen Peroxide and
Hydroperoxides in the Presence of Titanium
A break-through came when Enichem in Italy discovered
titanium silicalite (TS-I, a titanium-containing microp-
orous silica molecular sieve) as a catalyst for oxidations
with hydrogen peroxide.252 The company uses this com-
mercially for the preparation of cyclohexanone oxime (for
nylon 6) (4.52) and the oxidation of phenol to a mixture
of catechol and hydroquinone (4.53). It is building a 2000
metric ton/year plant to make propylene oxide by this pro-
cess (4.54).253 The selectivity to propylene oxide can be
as high as 100% at 0°C, 98% at 25°C, and 95% at
40°C.254 The selectivity was 93% when the hydrogen per-
oxide was generated in situ by oxidation of isopropyl al-
cohol with oxygen in the presence of a small amount of
lithium chloride.255 The by-product acetone can be hydro-
genated with hydrogen to produce more isopropyl alco-
hol. This may be a cheaper process than using premade
hydrogen peroxide. The reaction of cyclohexanone with
ammonia and hydrogen peroxide can also be done with
H-ZSM-5 zeolite coated with titanium silicalite giving
99% selectivity.256
The system can also be used to oxidize amines to
oximes with 88% selectivity at 40% conversion.257 The
substitution of other metals for titanium in the silicalite
gives catalysts that usually do not work as well. In any
90
4.54
event, titanium is less toxic than many others that could be
substituted for it.
The major limitation of titanium silicalite is the small
pore size, which restricts its use to small molecules. Its
discovery has spawned a great deal of work in many lab-
oratories to put the titanium into solids with larger pores.
Corma and co-workers have prepared titanium- and tita-
nium MCM-41 as large-pore zeolites.258 With these, the
epoxidation of 1-hexene to its epoxide with hydrogen per-
oxide was 96–99% selective. With tert-butylhydroperox-
ide the epoxidation was nearly 100% selective. The high-
est activity and selectivity for epoxidation of olefins with
organic peroxides was obtained when some of the silicon
atoms were substituted with methyl groups. Titanium-
-fluoride was more selective to epoxide than titanium-
hydroxide in the epoxidation of methyl oleate with hydro-
gen peroxide (95 compared with 80%). A bis(cyclopenta-
dienyl)titanium unit has been anchored in MCM-41 zeo-
lite. It gives 95% selectivity to the epoxide when
cyclohexene is oxidized with tert-butylhydroperoxide.259
A drawback of this catalyst is that it deactivates in 90 min
and must then be regenerated by heating to 550°C. A cat-
alyst made from titanium tetrafluoride and silica is said to
give better selectivity to the epoxide than the titanium ze-
olites because it contains no acidic sites.260 With it, cy-
clohexene was converted to its epoxide in 96% conver-
sion and 100% selectivity. The catalyst could be
recovered for reuse by centrifugation.
Microporous and mesoporous amorphous titanosilicates
have been made by the sol–gel method from tetraethoxysi-
lane and tetrapropyltitanate without amines.261 In contrast
with titanium silicalite with hydrogen peroxide, which
gives about equal amounts of catechol and hydroquinone,
4.55
Chapter 4
it produces about 90% catechol and 10% hydroquinone,
but the hydrogen peroxide efficiency is only 26%. With
other catalysts in this series, the hydrogen peroxide effi-
ciency went up to 93%, but then the products were 63%
catechol and 37% hydroquinone. Titanium-containing
amorphous glasses (with 0.7-nm–tubular pores) made by
the sol–gel method were used as catalysts for the reaction
of 1-hexene with tert-butylhydroperoxide to give the cor-
responding epoxide in nearly quantitative yield.262 The rate
did not slow down with higher -olefins, but did for higher
internal and cyclic ones. In some cases, alkyl or aryltri-
ethoxysilanes have been used in the sol–gel method for
high selectivity.263 In the epoxidation of E-2-hexen-1-ol
with tert-butylhydroperoxide in toluene and a titania–silica
catalyst, selectivity was improved to 90–98% by adding
sodium bicarbonate or zeolite 4A.264 These prevented un-
wanted ring opening of the product. A catalyst made by
treating silica with tetraisopropyltitanate gave good selec-
tivity in the epoxidation of olefins with tert-butylhydroper-
oxide at first, but after five uses the activity was only 68%
of the original, suggesting loss of some of the titanium.265
Soluble alkylsilasequioxanes substituted with titanium (a
cage structure of seven silicon atoms and one titanium
atom) (as well as related gels) have been studied as models
for titanium silicalite.266 Selectivity of epoxidation of cy-
clooctene with tert-butylhydroperoxide was more than
95%.
Hutter and co-workers made mesoporous amorphous ti-
tania–silica aerogels by the sol–gel method, including su-
percritical carbon dioxide extraction in the workup.267
These were used with cumenehydroperoxide to epoxidize
1-hexene in 95% selectivity and cyclohexene in 100% se-
lectivity. The authors state that their catalysts are superior
to titanium- and titanium MCM 41 for the oxidation of
bulky compounds such as limonene (4.55).
A catalyst made by treating silica with tetraisopropylti-
tanate was used with tert-butylhydroperoxide to produce a
mixture of the two epoxides from limonene in 90%
yield.268 It gave a 96% yield of the epoxide from 2-heptene.
Thus, the limitation of TS-1 catalyst to small molecules is
Toxic Heavy Metal Ions
4.56
4.57
being overcome. Microporous amorphous solids appear to
work as well as their crystalline molecular sieve counter-
parts.
F. Oxidation by Other Peroxy Compounds
Dioxiranes are good selective oxidants. Some -diketones
have been oxidized to alcohols (4.56) in 95% or higher
yield.269 The dioxiranes are made and used in solution. The
nickel catalyst speeds up reaction 4.56. Hydrocarbons can
be functionalized (4.57) in up to 92% yield in this way.270
A dioxirane phase-transfer catalyst, produced in situ with
potassium peroxymonosulfate, has been used epoxidize an
olefin to an epoxide (4.58) in up to 92% yield.271
Dimethyldioxirane converts N,N-dimethylhydrazones to
the corresponding nitriles in 94–98% yields in 2–3 min.272 It
has also been used to convert cycloctatetraene to tetraepox-
ides.273 A dioxirane analogue, a perfluorinated dialkylox-
aziridine, has been used to oxidize alcohols to ketones.274
Potassium peroxymonosulfate has been used in the Nef
reaction to convert 1-nitrohexane to caproic acid in 98%
yield.275 Replacement of the potassium ion by tetrabuty-
lammonium ion allows the oxidant to be used in acetoni-
trile and methylene chloride. (Less toxic solvents would be
desirable.) When this reagent was used with a manganese
catalyst, 1-octene was epoxidized in more than 99%
yield.276 It also converted ethylbenzene to acetophenone
with more than 99% selectivity.
4.58
91
Butylamine has been oxidized quantitatively to buty-
ronitrile by 3-chloroperbenzoic acid using a ruthenium
tetramesitylporphyrin catalyst.277 Dialkylsulfides can be
oxidized to the corresponding sulfoxides in 90% yield by
magnesium monoperoxyphthalate on moist bentonite clay
in acetonitrile.278 The inorganic support promotes the
reagent and allows for an easy workup. p-Toluenepersul-
fonic acid has been used to oxidize amines to their amine
oxides in 40–95% yields.279
G. Oxidation by Amine Oxides and Iodoso
Compounds
Methylcyclohexane has been oxidized to an alcohol using
an amine oxide with a ruthenium porphyrin catalyst
(4.59).280 Cyclohexane gave a 95% yield of a 6.7:1.6 mix-
ture of cyclohexanone and cyclohexanol.281 (This suggests
using hydrogen peroxide with a catalytic amount of 2,6-
dichloropyridine and a ruthenium zeolite or heteropoly-
metallate.) Manganese282 and iron283 porphyrins gave
lower yields. The same reagent system has been used to ox-
idize aromatic compounds to quinones.284 The yields were
good (up to 97%) only when a methoxyl group was present.
Ruthenium porphyrin catalysts have also been used with
pyridine-N-oxides to oxidize sulfides to sulfoxides and
olefins to epoxides.285
Iodosobenzene can be made by oxidation of iodoben-
zene to iodobenzenediacetate, followed by treatment with
92
4.59
base.286 It has been used with a manganese chelate and a
trace of pyridine-N-oxide to convert olefins to their epox-
ides.287 Sodium hypochlorite can be used in place of the io-
dosobenzene. Alcohols can be oxidized to the correspond-
ing aldehydes in 79–94% yields, with no overoxidation to
the carboxylic acids, by 2-iodosobenzoic acid.288 The prob-
lem with both the amine oxides and the iodoso compounds
is that they produce reduced by-products that will have to
be isolated and recycled to avoid waste.
H. Electrically Assisted Oxidations
The use of electricity in reactions is clean and, at least in
some cases, can produce no waste. Toxic heavy metal ions
need not be involved in the reaction. Hazardous or expen-
sive reagents, if needed, can be generated in situ where
contact with them will not occur. The actual oxidant is used
in catalytic amounts, with its reduced form being reoxi-
dized continuously by the electricity. In this way, 1 mol%
of ruthenium(III) chloride can be used in aqueous sodium
chloride to oxidize benzyl alcohol to benzaldehyde at 25°C
in 80% yield. The benzaldehyde can, in turn, be oxidized to
benzoic acid by the same system in 90% yield.289 The ac-
tual oxidant is ruthenium tetroxide. Naphthalene can be ox-
idized to naphthoquinone with 98% selectivity using a
small amount of cerium salt in aqueous methanesulfonic
acid when the cerium( III ) that forms is reoxidized to
cerium( IV ) electrically.290 Substituted aromatic com-
pounds can be oxidized to the corresponding phenols elec-
trically with a platinum electrode in trifluoroacetic acid, tri-
ethylamine, and methylene chloride.291 With ethyl
benzoate, the product is a mixture of 44:34:22 o/m/p-hy-
4.60
Chapter 4
droxybenzoates in 89% yield. Water is used to hydrolyze
the intermediate trifluoroacetate. In another case, electric-
ity is used to generate sodium hypoiodite and sodium hy-
droxide continuously for the epoxidation of 2-methylnaph-
thoquinone (4.60).292 The yield is 100%. No waste is
produced and no hazardous halogen has to be handled or
shipped. Unfortunately, the yield drops to 89% when
sodium bromide is substituted for the iodide, and to 6%
when sodium chloride is used. One wonders whether such
a process could be used to convert propylene to propylene
oxide economically. It would also be desirable to use a sol-
vent that is less toxic than acetonitrile. Propylene may be
soluble enough in just water for the reaction to be used.
I. Oxidation by Halogens and Halogen
Compounds
Iodine has been used to oxidize aldehydes to esters in alco-
hols (4.7) in 91–98% yields.293
RCHO 
I2
→ RCOOR 91–98% (4.7)
KOH in ROH
It is possible that the iodine and base could be generated in
the way cited earlier for the oxidation of 2-methylnaphtho-
quinone. Fluorine forms a hypofluorous acid–acetonitrile
complex when it is passed into wet acetonitrile. This com-
plex has been used to convert olefins, such as undecylenic
acid, oleic, and cinnamic acid to the corresponding epox-
ides in 90% yields.294 The disadvantages of the process are
the need to handle the very reactive fluorine and the need
to recycle the by-product hydrogen fluoride.
Sodium hypochlorite, as in household bleach, is an in-
expensive oxidant. In use, it does produce by-product
Toxic Heavy Metal Ions
4.61
sodium chloride, which, in theory at least, could be recy-
cled by electrolysis. It has been used to oxidize a variety of
olefins to their epoxides in the presence of manganese
chelates as catalysts, with yields of 80–95%.295 Quaternary
ammonium salts can be used as phase transfer catalysts.
Amine oxides are also added in catalytic amounts in some
cases. Manganese chelates of porphyrins and salicylidene
amines are used as catalysts. A typical example is shown in
Reaction 4.61. With optically active chelates, the oxidation
can be highly stereospecific. Alcohols can be oxidized to
aldehydes or ketones in 30 min at room temperature using
aqueous sodium hypochlorite, ethyl acetate, and tetrabuty-
lammonium bromide as a phase-transfer catalyst.296 Ben-
zaldehyde was obtained in 93% yield and octaldehyde in
86% yield. Alkyldimethylamines have also been oxidized
to amine oxides using sodium hypochlorite with iron–halo-
genated porphyrin catalysts.297 The presence of the 16
halogen atoms in the porphyrin stabilizes this ligand to ox-
idation. Ligand oxidation is a common problem limiting
the lifetimes of oxidation catalysts.
An ortho-dimethylbenzene has been oxidized selec-
tively to a toluic acid in a two-phase system in which the
product is extracted into water as it is formed (4.62). Three
equivalents of sodium hypochlorite are used with sodium
4.62
4.63
93
hydroxide, 1% ruthenium(III) chloride, and 5% tetrabuty-
lammonium bisulfate to produce the product in 98%
yield.298 The oxidation takes place in the organic phase.
This example illustrates the principle of removing the prod-
uct as it is formed, before further side reactions can take
place, so that a high yield can be obtained.
Upjohn and Pharmacia have used the steroidal interme-
diate, bisnoraldehyde, to make progesterone and corticos-
teroids for many years. Recently, they developed a new ox-
idation process for conversion of the primary alcohol to
bisnoraldehyde (4.63). This uses sodium hypochlorite
bleach with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidiny-
loxy radical in a two-phase system.299
The many advantages of the method over earlier ones
include no heavy metals, no noxious emissions, no haz-
ardous reagents or reaction mixtures, increased utilization
of the soya sterol feedstock (from 15 to 100%), elimination
of ethylene dichloride (a carcinogen) solvent, 89% less
nonrecoverable solvent waste, 79% less aqueous waste,
and the wastes are nontoxic. Presumably, a method for re-
cycling the expensive catalyst has been developed.
Periodates have been used in a variety of oxidations.
Tetrabutylammonium periodate can be used in nonaqueous
media to oxidize alcohols to aldehydes (60–97% yields),
94
mercaptans to disulfides (90–100% yields), and dialkylsul-
fides to sulfoxides (60–75% yields).300 Sodium periodate
has been used with ruthenium complexes as catalysts for
the oxidation of olefins to epoxides (45–99% yields) and
alcohols to ketones (75% yield). The epoxidation of the
olefins is complicated by cleavage of the carbon–carbon
bond.301 The reduced iodine compounds can be converted
back to periodate electrochemically. Sodium perbromate
with a ruthenium(III) chloride catalyst has been used to ox-
idize primary alcohols to either the aldehyde or the car-
boxylic acid in 90% yield, depending on the reaction con-
ditions.302
J. Oxidation with Dinitrogenoxide
Dinitrogenoxide (nitrous oxide) may be a useful, relatively
harmless oxidant if a good inexpensive source of it can be
found. It can be obtained from the by-product gases from
the oxidation of cyclohexanone by nitric acid in the manu-
facture of nylon. It can also be made from ammonium ni-
trate. It is said to offer a wider range of process safety than
oxygen.303 As mentioned earlier, benzene can be converted
to phenol in 100% selectivity using dinitrogen oxide with
FeZSM-5 zeolite at room temperature. Solutia is using this
process as part of a route to adipic acid for use in making
nylon. This transformation is also of considerable interest
to makers of phenol, for it would eliminate the by-product
acetone formed in the current process that is based on
cumene hydroperoxide. (Adipic acid can also be made
from glucose, without the need for cyclohexane, nitric acid,
or benzene, as described in Chap. 9.)
X. MISCELLANEOUS: ASBESTOS AS A
TOXIC MATERIAL
Asbestos fiber is a carcinogen that can cause lung cancer.
In earlier years when this was not known, the material
was used widely in insulation, fire suits, and so on, be-
cause it could not burn and was inexpensive. In friction
materials, it shows a high affinity for resins used with it,
good heat resistance, a high coefficient of friction, and
low abrasion.304 Many materials have been suggested as
replacements. The cheaper ones are natural minerals,
such as mica, talc, attapulgite, and vermiculite. Some-
what more expensive are glass and steel fibers. More
expensive yet are fibers of alumina and silica. Fibers of
organic polymers, such as polypropylene and polyacry-
lonitrile, are also suitable for some applications. Strong
aramide, carbon; and polybenzimidazole fibers are too
expensive for most applications. The replacement se-
lected will depend on the application. Filled polymers
Chapter 4
should be relatively simple, although it may require a hy-
drophobically-coated filler. Brake linings for cars and
trucks pose more of a challenge. These may require glass
or metal fibers or even aramide or graphite fibers. At one
time brake linings were the principal source of asbestos
fibers on city streets.
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RECOMMENDED READING
1. K.M. Dear. Top Curr Chem 1993; 164:115.
2. R.A. Sheldon. Top Curr Chem 1993; 164:21.
3. S. Wilson. Chem Ind (London), 1994:255.
4. C.R. Jolicoeur. Kirk–Othmer Encyclopedia of Chemical
Technology, 4th ed. 1992; 3:683–684.
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6. J. Muzart. Synthesis 1995:1325.
EXERCISES
1. How is the disposal of used fluorescent lamps and
batteries handled where you live? If they can re-
lease mercury and other heavy metals into the en-
vironment, devise a system that will not.
2. Check the Toxic Release Inventory (or a compara-
ble compilation) for releases of heavy metal ions
in your area. Suggest alternative chemistry that
could eliminate the releases.
3. What are the fish advisories in your area due to?
4. Keep a list for a week of the toxic metal ions that
can be found in your home, or car, or that you use
in the laboratory. Could any of the metal ions end
up contaminating the environment?
5. Check to see what biocides are in the products in
and around your home.
6. Is the current removal of asbestos from buildings
overkill?
7. Visit the physics or engineering departments on
102
campus to see what nonaqueous methods they use
to apply metal coatings.
8. What other reagents can you think of that might be
regenerated electrochemically to reduce the
amount of reagent needed?
9. Tabulate the oxidants used in an annual volume of
Organic Syntheses. How might environmentally
friendly oxidants be substituted for any that in-
Chapter 4
volve toxic metals or that produce large amounts
of waste salts?
10. What might be substituted for Ni–Cd batteries?
11. Visit some local industries that use toxic heavy
metal ions to see how they handle their wastes. In-
clude a visit to the local boat showroom to find out
what they recommend for antifouling paints.
5
Solid Catalysts and Reagents for Ease of Workup
I. INTRODUCTION
The most obvious advantage of a solid catalyst or reagent
is that it can be removed from the reaction mixture by sim-
ple filtration or centrifugation. This allows quick recovery
for reuse in the next run. Alternatively, the solid can be put
in a column with the reaction mixture flowing through it.
There can be other advantages as well. If the catalyst is ex-
pensive or toxic, this provides a way to not lose it and to
minimize exposure to it. If the bulk solid catalyst is expen-
sive, less of it will be needed if it is spread over the surface
of a solid support. The use of the solid material can mini-
mize waste. Consider, for example, the use of a strong acid
ion-exchange resin in place of p-toluenesulfonic acid to
catalyze an esterification. The resin can be recovered for
reuse by filtration. The p-toluenesulfonic acid has to be re-
moved by washing with aqueous base, after which it is usu-
ally discarded as waste. The solid catalyst can be used at
very high catalyst levels because it can be recovered and
used again. If the reaction is being performed on a solid
support, a large excess of another reagent can be used to
drive the reaction to completion. The excess reagent and
any by-products can easily be washed off the solid. The
vigor of some reactions can be moderated by putting a
reagent on a solid. However, this may involve the use of ex-
tra solvent to put it on to the solid and then to extract the
product from the solid. Some solids, such as clays and ze-
olites, offer size and shape selectivity, so that higher yields
and fewer by-products can be obtained. Some catalysts can
catalyze not only the desired reaction, but also side reac-
tions. Isolating catalytic sites on a support can sometimes
eliminate these side reactions. The support may also limit
the possible conformations of the catalytic site in a way that
limits side reactions. As an example, the immobilization of
some enzymes increases their thermal stability. Altus Bio-
103
logics, Cambridge, Massachusetts, does this by cross-link-
ing enzyme crystals.1
There are some disadvantages to the use of solid cata-
lysts and reagents. It may not be possible to obtain a high
loading, so that reactions are slower and more catalyst may
be needed. Particles with the high surface area needed for
the support to obtain higher loadings may not be very me-
chanically stable, and the catalyst may suffer from attrition
in use. DuPont has solved this problem for a vanadium py-
rophosphate catalyst, used in the oxidation of n-butane to
maleic anhydride, by putting a hard porous shell of silica
around it.2 The resulting particles are stable enough to be
used in a circulating fluidized bed. This has increased the
yield in the reaction. A polymeric support needs to swell in
the medium to allow the reaction to proceed. It may not
swell properly in some media. If the particles are too fine,
flow rates through the catalyst bed may be too slow.
Groups on the surface may be active, whereas those inside
the particle may not be accessible for reaction.
Table 5.1 compares the advantages and disadvantages
of homogeneous and heterogeneous catalysts.
Many books and reviews cover the preparation, charac-
terization4 and use of homogeneous5 and heterogeneous6
catalysts. Others describe supported metal catalysts,7 other
supported catalysts and reagents,8 and their use in prepara-
tive chemistry,9 the use of polymers as supports,10 trends in
industrial catalysis,11 and the environmentally friendly na-
ture of solid catalysts and reagents.12
The support may not be an innocent bystander. It may
act as a ligand for any metal compound put on its surface
and in doing so alter the steric and electronic properties of
the metal complex. Groups on its surface, such as hy-
droxyl and carboxyl, may react with the metal complex
added to produce a new compound. Binders to improve
mechanical stability and promoters to improve activity are
104
Table 5.1 Characteristics of Homogeneous and Heterogeneous Catalysts
Characteristic Homogeneous
Ease of separation May be difficult
Thermal stability Often low
Sensitivity to oxygen and moisture May be high
Life Low
Range of suitable solvents Limited
Corrosion and plating out Sometimes
Selectivity Often high and easy
to modify
Reproducibility High
Efficiency High (all sites active)
Source: Ref. 3. (Adapted from U. Schubert, New J. Chem., 1994, 18, 1049 with permission of Gauthier-Villars/ESME-23 rue Linois-Paris cedex 15 and
Elsevier.)
often added. An inert filler can also be used to dissipate
heat in exothermic reactions. The promoter may be an-
other metal ion which can then react with the first metal
ion to form a cluster.13 It can also promote by preventing
attrition of the solid. The surface of the solid will vary
with the coordinately unsaturated active sites being at
edges, corners, and defects. Putting the active catalytic
group right on the surface may not allow it to form the
right conformation for the desired reaction. In this case, a
spacer group of several atoms may have to be added. It is
occasionally possible to boost activity, as with some poly-
mers, by putting more than one functional group on the
surface to create a multidentate ligand. Enzymes are pro-
teins that often have several groups in widely different
parts of the molecule that curl around a metal ion to form
an active site. A low loading can isolate active sites so
that some deactivation reactions that involve two sites can
be prevented. Considering the various reactions that can
occur in putting the catalyst on the support, it is clear that
more than one type of site can be present. Sometimes, se-
lectivity to the desired product can be improved by poi-
soning one type of site. Selectivity can be improved by
using clays and zeolites that offer selectivity by size and
shape between layers in the former and in porous chan-
nels in the latter.
Heterogeneous catalysts can be deactivated in several
ways. A metal may be poisoned by a strong ligand (e.g., a
sulfur compound on a hydrogenation catalyst). Metal parti-
cles may sinter and agglomerate so that surface area is re-
duced. This process may be aided by reaction with one of
the reactants to form a different compound, as in palladium
hydride formation in hydrogenations. Site isolation can re-
duce this aggregation. The active catalyst may undergo
leaching of the active material, especially if strongly coor-
Chapter 5
Heterogeneous
Just filter
Usually high
Often low
Often high
Almost no limit
None
Less selective, several types of sites may
be presebt
Very dependent on mode of preparation
May be low (only sites on surface active)
dinating solvents or reactants are used. Coke often builds
up when catalysts are used at elevated temperatures.14 With
inorganic supports, it is common to regenerate such cata-
lysts by burning off the organic matter in oxygen at an ele-
vated temperature. Some promoters help prevent this
buildup of carbon. For example, the addition of some gold
to a nickel catalyst used in the steam reforming of hydro-
carbons eliminates the usual deactivation with time, appar-
ently by preventing the formation of graphite.15 When this
is a big problem, it is sometimes possible to cycle the cata-
lyst through the reaction vessel, then to a regeneration ves-
sel, and back to the reaction continuously. On the other
hand, there are times when some coking can passivate a
catalyst’s surface and lead to enhanced selectivity.16 Attri-
tion can be a problem, especially if fluidized beds are used
to avoid channeling.
The catalyst can be placed on the support in a variety of
ways. One common one is to coat the support with an aque-
ous solution of catalyst or its precursor, then to dry and, if
necessary, activate it by reduction, oxidation, or other such
reaction. Vapor deposition can also be used. Such materi-
als may not be held on strongly; thus, leaching can be a
problem in strongly coordinating solvents. The ionic bond-
ing that results when an ion-exchange resin picks up an an-
ion or cation will be stronger, as long as the pH is kept in
an acceptable range. The bonding will be stronger yet if a
stable chelate is formed. The most stable bonds for holding
the catalyst are covalent. And, of these, the best are those
that are resistant to the reaction being run, as well as to hy-
drolysis and oxidation.
Green chemistry provides a strong motivation to hetero-
genize homogeneous catalysts. With the proper chemistry,
it is possible to attach almost any catalyst to an inorganic
support, a magnetic bead, or a polymer. The rest of this
Solid Catalysts and Reagents
chapter will serve as a progress report on what has been
done and the many challenges that remain. Numerous ex-
amples from the recent literature will be used to illustrate
the range of possibilities. The use of inorganic and polymer
supports, as well as ion-exchange resins will be discussed
in this chapter. Clays and zeolites will be covered in the fol-
lowing chapter. Immobilized, enzymatic catalysts will be
discussed in Chap. 9.
II. THE USE OF INORGANIC SUPPORTS
When one places a reagent on to a support, it spreads out
into a thin accessible layer. If the reactant is now added, the
local concentrations of reactants may be high, thus favor-
ing a bimolecular reaction. This is also a way to bring to-
gether two reactants that may not be particularly soluble in
the same solvent. For example, one compound can be
placed on a support as a solution in water. Then, after dry-
ing, the solid can be treated with a reactant in a water-im-
miscible solvent. If the by-products of the reaction do not
interfere with the reaction, the support may be reloaded
with more of the reagent for use again. If they do, it may be
necessary to purify the support before it can be used again.
5.1
5.2
5.3
105
A few examples from the literature will serve to illustrate
some of the possibilities.
Sodium has been dispersed on the surface of alumina,
sodium chloride, or titanium dioxide by stirring with ex-
cess support at 180–190°C under argon. The first was the
most effective for reducing titanium(III) chloride for the
McMurray reaction 5.1, being better than the commonly
used reduction with zinc.17
The reagent is described as inexpensive, readily pre-
pared and nonpyrophoric, but air-sensitive. Sodium dis-
persed on titanium dioxide in a similar way has been used
to reduce zinc chloride to “active” zinc for reaction with
RX to give RZnX. This method produces fewer by-prod-
ucts from Wurtz coupling.18
Many organic reactions have been run on alumina.19
The hydrolysis of nitriles can be performed quickly on ex-
cess alumina (5.1). Further hydrolysis to the carboxylic
acid is slow.20
60°C
RCN on Al2O3 → RCONH2 82–92% (5.1)
Potassium permanganate on alumina has been used to oxi-
dize benzylic hydrocarbons to ketones (5.2), often in high
yields.21
Silica is another common support. Copper(II) nitrate on
silica (5.3) has been used to regenerate carbonyl com-
pounds from their oximes, tosylhydrazones, 1,3-dithi-
olanes, or 1,3-dithianes in 88–98% yields.22
Potassium fluoride on alumina is sometimes used as a
base.23 It may be that the fluoride ion displaces some sur-
face hydroxyl from the alumina to produce some potassium
hydroxide. Lithium chloride, bromide, and iodide on silica
106
5.4
have been used to open epoxide rings (5.4) to give the cor-
responding halohydrins.24
Some Wittig reactions (5.2) are much faster when the
aldehyde is put on silica first.25
 SiO2
hexane
(C6H5)3P C HCOOCH3  RCHO  → (5.2)
25°C.
RCH  CHCOOCH3  (C6H5)3PO
It is sometimes possible to eliminate some by-products
and increase yields of the desired products by putting the
dienophile on silica (5.6).26 Under standard conditions, the re-
action yields 51% of the desired product and 35% of the
dimethylamine adduct of the starting quinone. The reaction of
acetyl chloride with alkylene glycols on silica was 98–100%
selective for the monoacetate at 52–66% conversion.27
There are also some cases where the support is coated
with a homogeneous film that is insoluble in the medium.
Dibutyl sulfide was oxidized in methylene chloride to the
corresponding sulfoxide quantitatively with cerium ammo-
5.6
5.7
Chapter 5
nium nitrate in an aqueous film on silica.28 There was no
overoxidation to the sulfone. A polyethylene glycol film on
silica has been used with a water-soluble rhodium catalyst
in the hydroformylation of 1-hexene.29 The activity was as
good as in the comparable homogeneous system, and there
was little isomerization to 2-hexene. A 6:1 ratio of lin-
ear/branched isomers was obtained (5.7).
Palladium complexed with a water-soluble phosphine,
the sodium salt of triphenylphosphine-m-sulfonic acid, in
an aqueous film on silica catalyzed allylation in acetonitrile
in 100% conversion (5.8).30 No metal was lost. The catalyst
could be recycled.
A latex-supported catalyst has been used to isolate sites.
Styrene has been polymerized in the presence of an ionene
diblock copolymer (a water-soluble cationic copolymer) to
form a graft copolymer latex.31 The cobalt phthalocyanine
sulfonate catalyst [CoPc(SO3Na])4 was added and be-
came attached to the cationic polymer. When this catalyst
was used for the oxidation of thiols to disulfides by oxygen,
the activity was 15 times that in a polymer-free system.
Solid Catalysts and Reagents
5.8
5.9
This site isolation suppresses the formation of inactive
dioxygen bridged -peroxo complexes.
Hydroxyl groups are present on the surfaces of oxides
such as alumina, silica, titania, magnesium oxide, and such.
These can be used to anchor catalysts to supports. In one
case, the surface hydroxyl group was converted first to a
potassium salt by treatment with potassium acetate at pH
8.4, then to a cobalt salt with cobalt(II) chloride. This was
used as catalyst for the oxidation of phenols to quinones by
oxygen (5.9).32
An iridium complex was attached to a silica surface
without the use of any base (5.10).33 The silica behaves as
a simple ligand would.
5.10
5.11
107
A rhodium phosphine was anchored to silica as in
Eq. 5.3.34
B
M SiMOH  CH3Rh(P(CH3)3)2(CO) →
(5.3)
B
M SiMORh(PCH3)3)2(CO)  CH4
An allyltris(trimethylphosphine)rhodium complex with an
RhOSi linkage has also been prepared.35
Metal chlorides can also be put on oxide supports. Zinc
chloride was put on alumina in tetrahydrofuran, followed
by dilution with methylene chloride, then boiling with a
few drops of water and finally evaporation and drying. It
was used as a catalyst to prepare a diketone (5.11).36
108
5.12
This method prevented side reactions that occurred when
zinc chloride was used in tetrahydrofuran. With no zinc chlo-
ride at all, the reaction was sluggish. Metal chlorides, as well
as protonic acids, on such supports are sold by Contract
Chemicals in England as “Envirocats” (short for environ-
mentally friendly catalysts).37 They are stable to air. One of
them has been used to dehydrate an oxime to a nitrile (5.4).38
ArCHFNOH 
Envirocat EPZG
→ ArCN 67–92%
100°C., no solvent
(5.4)
The catalysts are non toxic powders that can be reused sev-
eral times. (Solid acids and bases will be discussed in detail
in Chap. 6.)
There is some question about the nature of the active
sites in these supported metal chlorides. One can envision
a number of structures that might result when zinc chloride
on silica is treated with water. (Similar structures might be
written for zinc chloride on alumina.) These might include
5.13
Chapter 5
the structures in 5.12. Other hydroxyl and chloride-bridged
structures might also be present.
A supported palladium catalyst for the Heck reaction
(5.13) could be reused several times with little loss in
activity.39 Heterogeneous catalysts for the Heck reaction,
such as palladium on silica and platinum on alumina can
perform just as well in the Heck reaction as homogeneous
catalysts.40
Reduction of rhodium(III) chloride with zinc borohy-
dride in the presence of silica produced a catalyst that gave
nearly 100% chemoselectivity to 2-phenylpropionalde-
hyde (5.14).41 No loss of the expensive rhodium occurred.
(Rhodium is expensive enough so that industrial processes
cannot afford to lose more than traces of it.)
The most common way to attach groups to metal oxide
surfaces is to treat the surface with alkoxysilanes that contain
other groups that can be reacted further to attach other things.
Methoxides and ethoxides are used commonly (5.15).
Solid Catalysts and Reagents 109

5.14

The product of the first reaction was added to a double then being used to treat silica, thus anchoring the calixarene
bond in a fullerene using a platinum catalyst.42 The amino to the support.50 Various chelating agents have been at-
group in the second product has been used to support tached to silica by such routes.51 When X was CH2Cl, it
peracids.43 The products have possible use in the disinfec- was possible to attach a salicyclideneamino chelating agent
tion of gases and in the treatment of wastewater containing which chelated manganese(III).52 The regular pore struc-
low levels of organic compounds. Another route to the ture of the mesoporous silica used was not disrupted in the
peracid involves hydrolysis of the nitrile to the carboxylic process. When X is CH2Cl, a cyclopentadienyl group can
acid, followed by conversion to the peracid with hydrogen be put on by reaction with cyclopentadienyllithium.53 This
peroxide. The peracid is then used to oxidize cyclic olefins has been used to pick up fullerenes which could be recov-
to their epoxides, with 96–100% selectivity at 55–62% con- ered later. It also provides a way to put in transition metal
version.44 The amino group in the aminopropylsilica has ions as metallocenes.
been used to attach a dye, by first treating with thiophosgene The process has also been used to attach photosensitiz-
to produce an isothiocyanate which reacted with an amino ers to silica.54 The product in Structure 5.16 was made by
group in the dye to form a thiourea.45 It has also been used treating aminopropylsilica with 2-hydroxy-1-naphthoic
to attach a platinum catalyst that was used to catalyze the ox- acid. It was more effective in the photochemical dechlori-
idation of cyclohexanol with oxygen to give cyclohexanone nation of polychlorinated biphenyls than a homogeneous
in 98% yield.46 In this last example, magnesium oxide could
be substituted for silica with equivalent results. A typical
way to add a metal catalyst is to complex it with a chelating
agent made from the aminopropylsilica and an aldehyde,
such as salicylaldehyde or 2-pyridinealdehyde.47 Rhodium
and palladium were attached at the same time to silica
treated with 3-isocyanopropyltriethoxysilane to produce a
catalyst for the reduction of arenes at 40°C at 1 atm hydro-
gen.48 The activity was higher than any yet reported for
other homogeneous or heterogeneous catalysts.
The product where X contained phosphorus was used to
complex nickel compounds.49 In another instance, tri-
ethoxysilane was added to an allylcalixarene, the product 5.16

(where X can be CN, CH2 NH2, CH2P(C6H5)2 and such)

5.15
110
5.17
sensitizer. Aminopropylsilica has also been used to attach
enzymes (5.17). The aminopropylsilica is treated first with
glutaraldehyde, then the enzyme.
Galactosidase has been attached to glass in this way.56
The immobilized enzyme is useful in removing lactose from
milk, for the benefit of those persons who are intolerant of
lactose. A similar technique was used to attach glucose ox-
idase to magnetite (Fe3O4) particles, starting with a
trimethoxysilane.57 This permits easy separation with a
magnet. The immobilized enzyme was 50% less active than
the native enzyme, but kept 95% of its activity after 9
months at 4°C. Another way to attach an enzyme to a sup-
port is to treat the metal oxide support first with 2,4,6-
trichloro-1,3,5-triazine (cyanuric chloride) (5.18), then with
the enzyme.58 This was done on both alumina and on silica.
A lipase immobilized in this way retained 80% of its ac-
tivity after 336 h. The catalyst could be reused three times
before its activity dropped to 50% of the original value and
it was still yielding more than 90% enantiomeric excess of
S()-2-arylpropionic acids. An enzyme from Candida
5.18
5.19
Chapter 5
cylindracea immobilized on silica in a similar way was 37
times more stable than the native enzyme. It retained 80%
of its activity after 336 h. Loss of activity on ageing or use
is a problem with many enzymes. (Biocatalysis is dis-
cussed in more detail in Chap. 9.)
Another way to attach groups to silica involves sequen-
tial treatment of the silica with tetrachlorosilane, diethy-
lamine, and 3-hydroxypropyldiphenylphosphine (5.19).59
This method was used to attach nickel and rhodium to
glass, quartz, and silica surfaces.
Similar techniques have been used to incorporate silica
into various polymers. (Mineral fillers are often given hy-
drophobic coatings to help in their dispersion in polymers
such as polyolefins.60) Methacrylatopropyltrimethoxysi-
lane has been used to add the methacrylate group on to sil-
ica. The treated silica was used in the emulsion polymer-
ization of ethyl acrylate.61 Transparent films could be
formed from the product. Living polystyrene was end-
capped with a triethoxysilane (5.20), after which it was
used to treat silica and alumina.62
Solid Catalysts and Reagents
5.20
The authors were interested in using this technique to
disperse inorganic pigments. A living polymer has also
been end-capped by treatment with chlorosilanes contain-
ing protective groups that were later removed to give ter-
minal hydroxyl and amino groups (5.21).63 A ruthenium
complex was made from the final amine.
A copolymerization of styrene, divinylbenzene, and
maleic anhydride was carried out in the presence of silica.
This was hydrolyzed in boiling water, then treated with
chloroplatinic acid to add platinum on silica.64 Presumably,
the anhydride reacted with the hydroxyl groups on the sur-
face of the silica. Then the platinum(II) formed a salt with
some of the carboxyl groups.
Another way to insert a noble metal catalyst on to silica
is as follows (5.5):
B ide or a mixture of metal oxides. The advantage is that the
M S iOH  P(CH2OH)3 →
Rh4(CO)12 (5.5)
B
M S iOCH2P(CH2OH)2 →
When used in the hydroformylation of propylene, this cata-
lyst was as good as Rh(H)(CO)(P(C6H5)3)3. It gave a 1:1
mixture of n-butyraldehyde and isobutyraldehyde,65 com-
pared with 3:1 for the reaction in solution. The linear alde-
hyde is more valuable, but a number of uses have been de-
veloped for the isobutyraldehyde. If the market needed
more of the latter, this might be an excellent way to make it.
5.21
5.22
111
The gradual evolution of catalysts for olefin polymer-
ization was described in Chap. 1. The use of magnesium
chloride as a support for titanium tetrachloride led to high
mileages that allowed the catalyst residues to be left in the
polyolefin.66 The polymer particle is an enlarged replica of
the catalyst particle. To make the desired compact granules
of polymer with a high bulk density (0.50 g/cm3 or higher),
the catalyst must be compact at the same time that it has a
high surface area. Newer metallocene catalysts are soluble
in hydrocarbons. To obtain the desired polymer morphol-
ogy, they must be put on supports, such as alumina, silica,
or zeolites.67
The sol–gel route has been used to heterogenize homo-
geneous catalysts.68 In the process, one or more metal
alkoxides are gradually hydrolyzed to produce a metal ox-
second metal oxide is found throughout the first one, rather
than just on the surface, as could result from treatment of a
preformed metal oxide support.69 In other cases, the transi-
tion metal catalyst is just entrapped physically by being
present during the hydrolysis of the tetraalkoxysilane.70
The method can be run to give high-surface areas which
can increase catalytic activity. A recent example involves
the cohydrolysis of two alkoxy silanes in the presence of
alumina (5.22).71
112
5.23
The resulting coating imparted “extremely high” scratch
resistance to plastics. This could result in longer-lasting
plastic eye glass lenses and dinnerware. Current materials
are limited by the tendency to scratch easily, and for din-
nerware, to stain.
The sol–gel method has also been used to put a
NHC(S)NHC(O)Ph on to silica.72 A rhodium catalyst made
from this could be used at least five times in the hydro-
formylation of styrene. By including some methyltri-
ethoxysilane in the cohydrolysis of tetraethoxysilane and
titanium(IV) isopropoxide, it was possible to vary the sur-
face polarity of the amorphous microporous mixed oxide
catalysts used in oxidations with hydrogen peroxide.73 The
methyl groups slowed the deactivation of the catalyst and
made it possible to regenerate them thermally.
Colloidal metal clusters, which offer a high surface area
for better activity, have been stabilized by polymers. Thus,
a homogeneous dispersion of a cobalt-modified platinum
cluster was stabilized by a coordinating polymer, poly(N-
vinyl-2-pyrrolidone).74 Addition of the cobalt(II) [or
iron(III)] doubled the activity and increased the selectivity
from 12 to 99% when the catalyst was used to reduce cin-
namaldehyde (5.23).
The system was very sensitive to the transition metal ion
added to the platinum. When it was nickel, hydrocin-
namaldehyde was obtained in 97% selectivity.75 The inter-
mediates in these reductions are probably metal hydride
clusters. When the colloidal platinum is supported on mag-
nesium oxide, without another transition metal, the reduc-
tion produces the unsaturated alcohol with 97% selectiv-
ity.76 A rhodium colloid stabilized by the same polymer
was used with a water-soluble phosphine in the hydro-
formylation of propylene to produce 1:1 mixture of n-bu-
tyraldehyde and isobutyraldehyde in 99% yield.77 It could
be used at least seven times, as long as it was not exposed
to air.
Colloidal palladium can also be stabilized with poly(N-
vinyl-2-pyrrolidone).78 Other polymeric stabilizers have
also been used with palladium, platinum, and other met-
als. These include poly(2-ethyl-2-oxazoline),
poly(methacrylic acid),79 block copolymers containing
COOH groups,80 poly(N-isopropyl acrylamide),81 and
poly(styrene-b-4-vinylpyridine).82 Colloidal iron has been
stabilized not only by poly(N-vinyl-2-pyrrolidone) but
Chapter 5
also by oleic acid.83 Such ferrofluids are of interest for
magnetofluid seals and bearings, as well as for other uses.
Palladium and rhodium catalysts have also been sup-
ported on dendrimers containing amine and phosphine
groups.84 Dendrimers are spherical polymers made start-
ing with a multifunctional molecule that is reacted with a
reagent that gives a product for which each new end be-
comes difunctional. This process is repeated several times
to produce the spherical polymer.85 A silicon-based den-
drimer was made and fitted with dimethylamino groups
that complexed nickel. The complex was used as a cata-
lyst for the addition of carbon tetrachloride to methyl
methacrylate.86 The dendrimer offers a controlled disper-
sion of the catalytic sites on the surface of the nanoscopic
particle with easy recovery for reuse. Copper can also be
placed in the voids inside polyamidoamine dendrimers
with 4–64 copper atoms per particle.87
Various workers have been making cluster compounds
to bridge the gap between homogeneous catalysts and their
heterogeneous counterparts. Platinum–rhenium clusters
have been made as models for bimetallic catalysts.88 It is
hoped that this will shed light on some of the promoter ef-
fects found when a second metal is added to catalysts. The
authors feel that the selective ligand displacement at rhe-
nium is relevant to the mode of action of heterogeneous
Pt/Re catalysts. The ligand in the clusters is Ph2PCH2PPh2
(5.24).
Roesky and co-workers have used reactions of silanetri-
ols to produce a variety of metallasiloxane cage struc-
tures.89 Some of these are shown in 5.25. An aluminum
silasesquioxane has been made as a model for silica-sup-
ported catalysts. It catalyzed (1 mol%) a Diels–Alder reac-
5.24
Solid Catalysts and Reagents 113

5.25

tion between a diene and an unsaturated ketone (5.26).90

Titanium analogues have also been made.91
Silsesquisiloxanes are made by the hydrolysis of tri-
alkoxysilanes or trichlorosilanes.92 The octameric units are
similar to structures in zeolites. They also model a silica
particle. Some have been inserted into polymers. In one
case four methacrylate groups have been added to an oc-
tameric structure (5.27).93
The product polymerized readily with heat or light to a
polymer containing 65% silica. An octameric
silsesquisiloxane has also been appended to polystyrene
(5.28).94
5.27

5.26
114
5.28
III. ION-EXCHANGE RESINS
Ion-exchange resins95 have been used for many years,
mainly to remove unwanted ions from water. For example,
calcium and magnesium ions in hard water can be removed
in this way. A two-bed system of a strong acid cation-ex-
changer followed by a strong base anion-exchanger can be
used to deionize water, as an alternative to distilled water.
Electrodeionization of copper ion-containing wastewater
using alternate cation- and anion-exchange membranes can
be used to recover copper and very pure water for recycle
to the electroplating plant, so that there is no waste.96 (Re-
covery of metal ions from wastewater from metal-finishing
plants was discussed in Chap. 4.) A weak base ion-ex-
changer has been used to recover acetic acid from a 1%
aqueous solution.97 Thus, the resins can be used to recover
valuable chemicals from wastestreams before the water is
discharged from the plant. The resins can also be used as
insoluble catalysts or reagents before or after further mod-
ification. Because of microenvironmental effects and
site–site interactions, polymer-supported reactions may
differ from their homogeneous counterparts in course of
the reaction, selectivity, rate, and stereochemical results.98
This can sometimes be very advantageous. Before describ-
ing such uses, a brief summary of what the resins are and
how they are made will be given. This will focus mainly on
those derived from polystyrene.
Styrene containing some divinylbenzene and a water-
immiscible solvent as a porogen are polymerized in aque-
ous suspension using a free radical initiator. When done
properly, this results in a sturdy bead containing pores
where the solvent used to be. This macroreticular resin has
more surface area and, after derivatization, a much greater
exchange capacity than a solid bead of the same size. Re-
cent work has shown how to improve the beads by making
Chapter 5
them monodisperse.99 The method uses monodisperse seed
from an emulsion polymerization for the following suspen-
sion polymerization. The reactions (5.29) to form the actual
ion-exchange resins from this support are shown.
The use of dimethylamine in place of trimethylamine
would produce a tertiary amine. Pyridine has also been
used in the quaternatization to produce anion-exchange
membranes.100 (Membranes are covered in Chap. 7.) The
amount of divinylbenzene in the polymerization can be
varied widely, but for use in water it is about 8%. Com-
mercial beads are about 0.3–1.2 mm in diameter.
There are other ways to obtain some of these products.
Efforts have been made to replace the formaldehyde–hy-
drogen chloride mixture, which is carcinogenic. One
method uses trioxane with trimethylchlorosilane and
tin(IV) chloride.101 Another copolymerizes 4-vinylbenzyl
chloride with divinylbenzene. Still another copolymerizes
4-vinyltoluene with divinylbenzene, then chlorinates the
methyl group with sulfuryl chloride102 or cobalt(III) acetate
in the presence of lithium chloride.103 Aminomethyl
groups have been introduced into the styrene–divinylben-
zene copolymer by treatment with N-chloromethylphthal-
imide and iron(III) chloride, followed by removal of the
protecting phthaloyl group.104 Acylation of cross-linked
polystyrene with acetic anhydride, followed by reductive
amination of the ketone, yielded a 1-aminoethyl-
polystyrene.105 Quaternization of this amine with
iodomethane gave an anion-exchange resin. A greener
method would be to quaternize with less toxic dimethyl
carbonate.
The functional group can also be introduced in a
monomer used in the original polymerization. Sulfonic
acids can be introduced as their sodium salts with sodium
4-vinylbenzenesulfonate. In one case, this was used with
N,N-dimethylacrylamide and methylenebis(acrylamide) as
Solid Catalysts and Reagents
5.29
comonomers.106 Sodium 2-sulfoethyl methacrylate was
also used to add the sulfonic acid. Hollow polyethylene
fibers grafted with sodium 4-vinylbenzenesulfonate were
as effective (after conversion to the acid form) in acid-cat-
alyzed reactions as the usual beads of ion-exchange
resins.107 Weak acid resins can be made by copolymeriza-
tion of monomers, such as acrylic acid, methacrylic acid,
and maleic anhydride, with a cross-linking monomer.
The chloromethyl group can be modified to introduce
chelating groups for more specific ion exchange108 (e.g., by
reaction with ethylenediamine,109 glycine,110 or the sodium
salt of iminodiacetic acid). The product from ethylenedi-
amine could be used for complexation of copper(II) ion. It
was also used to scavenge carbon dioxide, which could be
recovered later by thermal desorption.111 Some metal ion
separations are helped by putting both sulfonic and phos-
phonic acid groups in the resin (e.g., europium(III) from ni-
tric acid).
The acidities of the cation-exchange resins fall in the
following order: SO3H  PO3H2  PO2H2  COOH. The
quaternary ammonium base is stronger than the tertiary
amine base. The efficiency of columns of beads is in-
creased by small, uniform particle size, low degree of
cross-linking, high temperature, low flow rate, low ionic
concentration in the incoming liquid, and a high length/di-
ameter ratio. In practice, these must be balanced against
cost and time. It is desirable to have the resin denser than
the liquid. The resin must swell to be active, so that the de-
gree of cross-linking should not be too high. This swelling
also means that some extra room has to be left in the col-
115
umn for this. There are several ways that the resins can
wear out. These include attrition in use, in part due to
swelling and shrinking; oxidation by air, chlorine, hydro-
gen peroxide, and such; thermal degradation; radiation;
desulfonation; and fouling. The use of quaternary ammo-
nium hydroxide resins may be limited to 40–100°C. When
radioactive solutions are involved, inorganic exchangers
are used.112
Sulfonic acid resins can be used as solid catalysts for
esterifications and other acid-catalyzed reactions. Am-
berlyst 15 was a more effective catalyst for the prepara-
tion of esters of phenethyl alcohol and cyclohexanol than
sulfated zirconia, an acid clay, and dodecatungstophos-
phoric acid.113 (Amberlyst and Amberlite are trademarks
of Rohm & Haas.) (See Chap. 6 for more detail on solid
acids and bases.) The same catalyst gave 86–96% yields
of hydroxyesters when a lactone was stored with a hy-
droxyacid.114 Diols can be monoacylated in 58–92%
yields by transesterification with ethyl propionate in the
presence of Dowex 50W (a product of the Dow Chemical
Co.).115 Modification of the sulfonic acid resin with 2-
mercaptoethylamine produced a catalyst for the reaction
of phenol with acetone to produce bisphenol A (5.30) in
99.5% yield.116 After 20 cycles the yield was still 98.7%.
When used as catalysts, ion-exchange resins can last for 6
months to 2 years.
Anion-exchange resins can be used as reagents.242 They
are commercially available with acetate, borohydride, bro-
mide, chloride, dichromate, iodide, and periodate anions.
Metal carbonyl-containing anions such as Co(CO) 4 ,
116 Chapter 5

An anion-exchange resin in the fluoride form has been

used to remove the tert-butyldiphenylsilyl protecting group
from an alcohol.128 A resin with bromate ion has been used
as an oxidizing agent.129 The resin was regenerated for
reuse by washing with aqueous sodium bisulfite, sodium
5.30 chloride, then exchange with sodium bromate. A resin with
the sulfhydryl ion was used to produce mercaptans from
alkyl halides.130
Rh(CO)I 2 and (Pt15(CO)30)
2
have also been used.117 A Nucleophilic substitution of the chloromethylated
polystyrene-based anion-exchange resin in the chloride cross-linked polystyrene resin has been used to attach a
form reacted with rhodium(III) chloride to produce a cata- wide variety of groups. Among these are those shown
lyst for hydration of acetylenes and for double-bond mi- (5.31): Potassium diphenylphosphide was used to make the
gration in allyl compounds.118 It was leach-proof and recy- first phosphine.131 The microenvironmental effects of this
clable. It might replace the more dangerous mercury catalyst in the formation of benzyl benzoate by the Mit-
catalysts sometimes used in hydration of acetylenes.
Copolymers of acrylamide and 3-(acryloylamino)propy-
ltrimethylammonium chloride have been used to bind
(PtCl6)2 for later reduction to platinum metal to produce a
hydrogenation catalyst.119 Strong base-exchange resins
have been used with sodium borohydride and nickel acetate
to reduce aromatic aldehydes to arylmethyl compounds in
78–98% yields,120 aryl oximes to benzyl amines,121 and
olefins to their saturated analogues.122 Monosubstituted
olefins were reduced quantitatively in 1 h at 0°C. Di- and
trisubstituted olefins were not reduced under these condi-
tions. When the reaction was carried out at 65°C for 1 h, the
disubstituted olefins, but not the trisubstituted ones, were
reduced. The resin was recycled by rinsing with dilute hy-
drochloric acid, then treating it with aqueous sodium boro-
hydride. Thioacetates were reduced to thiols with a boro-
hydride resin used with palladium acetate.123 Amine oxides
were reduced to the corresponding amines using a borohy-
dride resin with a copper sulfate catalyst in 93–96%
yields.124 Polymeric ozonides have been reductively de-
composed with a borohydride resin.125 Zinc borohydride
on a solid aluminum phosphate has been used to reduce
epoxides to the corresponding alcohols in 97% yields.126
Zirconium borohydride on cross-linked poly(vinylpyri-
dine) has been used to reduce carbonyl compounds without
touching the olefinic double bond in yields of 80–96%.127
The resin was regenerable by washing with acid and then
base, then treating again with zirconium borohydride. This
illustrates the diversity of supports that can be used with
borohydride ion. Each of these methods produces waste
salts. It would be better to reduce catalytically with hydro-
gen using supported metal catalysts, such as palladium on
charcoal, platinum on alumina, and such, if the desired se-
lectivity can be obtained. In the reduction of the thioac-
etates, it would be necessary to use a less active metal sul-
fide catalyst to avoid poisoning. Catalytic reduction would
avoid not only the waste salts, but also the high cost of the
reagents. 5.31
Solid Catalysts and Reagents 117

5.32

sunobu reaction (5.6) were studied at 18, 40, 67, and 100%
substitution. The yield and purity of the product were 5.32a
higher at the two lowest levels. The yield of 97% compared
favorably with the 85% obtained with homogeneous coun-
terpart. sumably owing to isolation of the active sites. The catalyst
was easy to recycle without loss of activity. It could be han-
C6H5COOH  C6H5CH2OH dled in air and had high thermal stability. The supported ti-
 C2H5OOCNBNCOOC2H5  polymeric phosphine tanium tartrate was used as a catalyst for the Diels–Alder
reaction of cyclopentadiene with methacrolein.140 It was
→ C6H5COOCH2C6H5 far more active than a homogeneous catalyst owing to site
 C2H5OOCNHNHCOOC2H5  phosphine oxide isolation. It could be recovered and reused.
Polymeric counterparts of 4-dimethylaminopyridine
(5.6) have been prepared by several groups. Reilly Industries sells
A palladium catalyst derived from this polymeric phos- one as Reillex PolyDMAP (5.32a).141 When used in esterifi-
phine gave yields almost identical with its homogeneous cations, the polymeric catalyst offers easy separation, re-
counterpart in Reaction 5.32. There was no decrease in ac- duced toxicity and the ability to use it in excess. It can be
tivity after five cycles of use.132 reused. The monomeric reagent is highly toxic. The two
Alcohols were added to the dihydropyrans.133 The furan other polymeric analogues of 4-dimethylaminopyridine
derivative was used in a Diels–Alder reaction with a (5.33) are based on other chemistry.142 The first is a
fullerene.134 Magnesium was added to the anthracene polyamide, the second, a polyurethane. In the second case,
derivative, after which it was used to prepare benzyl and al- glycerol was also sometimes added to produce an insoluble
lyl magnesium chlorides. The ability to take up magnesium product.
diminished over several cycles of reuse.135 Polymeric non- Another has been formed by the reaction of an alternat-
linear optical materials were made by reaction of ing copolymer of ethylene and carbon monoxide with 4-
chloromethylated polymer with the substituted pyridine to aminopyridine to form a polymeric pyrrole.143 Reaction of
form a quaternary ammonium salt, and also by reaction
with variously substituted alkoxides.136 The guanidine was
used to catalyze the reaction of soybean oil with methanol
to give the methyl ester.137 The catalyst was almost as ac-
tive as a homogeneous one. There was some leaching after
nine catalytic cycles, perhaps owing to displacement of the
guanidino group by methanol. An effort to avoid this by
adding five more methylene groups between the aromatic
ring and the nitrogen gave a less active catalyst. The cy-
clopentadiene derivative was used to prepare a rhodium
metallocene for use as a catalyst in the carbonylation of a
diene.138 The diphosphine was complexed with palla-
dium(II) chloride for use in the Heck reaction of iodoben-
zene with methyl acrylate to form methyl cinnamate (as
shown earlier in this chapter with a different supported cat-
alyst).139 The palladium had a much higher turnover num-
ber than that in a monomeric palladium counterpart, pre- 5.33
118
5.34
4-aminopyridine with epichlorohydrin produced another
analogue.144
A nonionic cross-linked polymethacrylate resin (Am-
berlite XAD7) was used in the reduction of the ketone
(5.34) by an aqueous suspension of Zygosaccharomyces
rouxii cells.145 Adsorption by the resin kept the concentra-
tions of the substrate and product below levels that would
be lethal to the cells, yet allowed enough to be in solution
for the reduction to take place in 96% yield with more than
99.9% enantiomeric excess (often abbreviated %ee).
IV. COMBINATORIAL CHEMISTRY
Merrifield pioneered the solid-phase method for the prepa-
ration of polypeptides.146 The typical support used is a
chloromethylated polystyrene cross-linked with 1% di-
vinylbenzene. A generalized scheme is shown (5.35).
R is typically 9-fluorenylmethyl or tert-butyl. In the for-
mer compound, the protecting group can be removed with
piperidine; in the latter one with trifluoroacetic acid. The
cycle of deprotection and coupling can be repeated many
5.35
Chapter 5
times to produce polypeptides. The general requirements
are that the reagents used in the synthesis and deprotection
steps not cleave the tether or the polypeptide. The final
cleavage removes both the support and the protecting
group. Over the years, many variations have been devised
to perform the cleavages under milder conditions. The big
advantage of the method is the ease of removal of unre-
acted reagents and by-products by simple washing. Large
excesses of reagents can be used to speed up the reactions
and ensure completion of reactions. In a study of the prepa-
ration of peptide guanidines, the solid-phase method of-
fered several advantages. The reaction was seven times as
fast as in solution. The yields were improved greatly. Prob-
lems with the solubility of reagents were eliminated, be-
cause a wider choice of solvents for the guanylation reac-
tion was now possible.147 Another recent innovation is the
use of ultrasound to assist the coupling of zinc carboxylates
with the Merrifield resin.148 Ultrasound also accelerated
the cleavage of the final polypeptide from the resin by
ethanolamines and aqueous sodium carbonate or sodium
hydroxide. The process involves an initial transesterifica-
tion, followed by hydrolysis of the new ester.
Combinatorial chemistry uses such methods to make
mixtures of many possible compounds (called libraries)
that can then be screened for the desired property to select
those compounds that are active.149 The methods are suit-
able not only for polypeptides, but also for oligonu-
cleotides,150 oligosaccharides,151 and a variety of small
molecules, including many heterocyclic compounds. The
method’s popularity is because our knowledge of the inter-
Solid Catalysts and Reagents
actions of molecules with receptors is not sufficient to al-
low prediction of the optimum structure. The changes in
conformations of both the ligand and the receptor during
complexation can be hard to predict. In addition, several
weak interactions can sometimes combine to provide
strong binding. The method can also uncover new unnatu-
ral structures for biological targets. This is a shotgun
method that works.
A popular method is the split-and-mix one. The first
reagent is attached to the support. The beads are then split
into several batches, each of which receives a different
building block. All the batches are recombined and again
split into several lots, each of which receives a different
added building block. This process is continued until the
desired library of hundreds or thousands of compounds is
complete. This method is good for making small amounts
of a large number of compounds. A second method, paral-
lel synthesis, makes a smaller library, but with larger
amounts of each compound. In this method, multiple reac-
tion vessels (e.g., a multiwell plate) allow the preparation
of a different compound in each well. Both methods have
been automated.
The libraries are then screened against the desired target
to pick out the active compounds. Sensitive methods are
needed, for the amount of a compound is small. High
throughput robotic screening is common. For example, po-
tential catalysts for exothermic reactions have been
screened by infrared thermography.152 In another example,
catalysts for hydrosilylation were screened by the bleach-
ing of unsaturated dyes.153 Sometimes it is not necessary to
remove the compound from the support before screening.
When an active compound is found, it must be identi-
fied.154 In parallel synthesis, this is not a problem, because
the well number will have its history recorded. With split
synthesis, it may be necessary to repeat the synthesis,
checking smaller and smaller sublibraries until the active
compound is found. Colored beads and vial caps have been
used to keep track of the reactions.155 An elegant way to
identify the beads is to start with beads in a tiny porous
polypropylene capsule that also contains a radiofrequency-
encodable microchip that can record each step in the pro-
cess.156 Matrix-assisted laser desorption/ionization–time
of flight (MALDI-TOF) mass spectroscopy has been used
to identify compounds from single beads.157
This method is especially useful because it can be used
with very small amounts of compounds with molecular
weights as high as several thousand.158 If the compound is
attached to the support by a photolabile link, the bead can
be analyzed without prior cleavage of the compound from
it. Solid-state nuclear magnetic resonance159 and infrared
microspectroscopy160 have also been used for compounds
on single beads.
119
5.36
Screening of the first library may not reveal a compound
with strong activity. If one with weak activity is found, a
new library can be made around it. This process may have
to be repeated several times before a compound with strong
activity is found.
The Merrifield resin does have some limitations. Be-
cause it does not swell in some solvents, reaction rates can
be low. This has led to a search for other more polar resins.
A variety of polyethylene glycol units161 have been put in
supports by different methods. One method is to attach a
polyethylene glycol chain to the cross-linked polystyrene
by graft polymerization, or other means.162 The polyethy-
lene glycol chains are free to move about because all the
cross-linking is in the polystyrene part. Such copolymers
have also been used as solid-phase–transfer catalysts, such
that they can be recovered for reuse by simple filtration.163
In another method, cross-linking of the polystyrene has
been done with tetraethylene glycol diacrylate instead of
divinylbenzene.164 Another resin has been made by
copolymerizing a polyethylene glycol end-capped with
acrylamide groups with N,N-dimethylacrylamide and N-
ethoxycarbonylethyl-N-methylacrylamide, then modifying
the resin to incorporate a benzyl alcohol group to produce
a highly porous, high-capacity resin (5.36).165
Cross-linked supports have also been made by copoly-
merization of polyethylene glycol terminated with
methacrylate groups with cross-linking agents such as
trimethylolpropane trimethacrylate.166 This type of resin
has also been used as phase-transfer catalysts.167
Solid supports tend to have low loading. To avoid this
problem, soluble polymeric supports have been used in so-
lution.168 The only requirement is that there be an easy way
to remove excess reagents and by-products at each stage.
Polyethylene glycol monomethyl ether has been used for
this purpose.169 Purification at each stage is achieved by ul-
trafiltration or by precipitation with a large amount of ethyl
ether or ethanol.170 Modified versions (5.37) have been
used in the synthesis of oligosaccharides.171
Purification at each step was achieved by fast column
chromatography in ethyl acetate. The polymer stays at the
top of the column while the reagents and by-products pass
through. The polymer is then eluted with 4:1 ethyl acetate-
methanol. Another system is to remove excess reagents and
by-products with solid polymeric reagents that react with
120
5.37
them; which enables separation by filtration. For example,
a polymeric amine can be used to remove isocyanates, acyl
chlorides, and sulfonyl chlorides. A polymeric base can be
used to remove hydrochloric acid. A polymeric isocyanate
can be used to remove amines.172
Ligands have also been attached to polyethylene glycol
so that they can be recovered for recycle by the foregoing
methods. A phosphine isocyanate has been reacted with
polyethylene glycol for use in the Staudinger reaction with
alkyl azides to form a phosphine imine.173 An alkaloid has
been attached to the monomethyl ether of polyethylene gly-
col for use in the Sharpless asymmetrical dihydroxylation
of olefins. The reaction was complete in the same time,
with no decrease in yield or enantioselectivity, as when the
alkaloid was used by itself.174 (Asymmetrical reactions are
covered in Chap. 10.)
Combinatorial chemistry has also been applied to the
preparation of catalysts175 and to inorganic compounds.176
New catalysts for the oxidation of methanol in fuel cells,177
the polymerization of olefins,178 and asymmetrical organic
reactions (or chiral recognition).179 have been found by this
method. A rate enhancement of 1 million for the ring-open-
ing hydrolysis of an isoxazole (5.38) was found with a
“synzyme” made by alkylating poly(ethylene imine) with
three different groups.180
Among the inorganic materials under study by this
method are phosphors,181 superconductors, magnetic mate-
rials,182 thin-film dielectric materials,183 pigments,184 and
zeolites.185 Many of these use magnetron sputtering of one
or more elements at a time on to a substrate through a se-
ries of masks. Combinatorial chemistry should also be ap-
plied to optimization of ligands (plain or polymeric) for the
separation of metal ions. Better separations are needed by
the mining, metal finishing, and other industries.
5.38a
Chapter 5
Combinatorial chemistry offers a good way to find a
new material while operating on a small scale. Thus, it does
not produce much waste. However, if the synthesis of the
new compound is scaled-up, there will be a problem with
wastes. Ways will need to be found to recycle excess
reagents, to minimize use of solvents and, if possible, to de-
velop ways to do without protecting groups.
Combinatorial methods are also being used in biology.
Beetles have been making mixtures of large-ring
polyamines as defensive secretions for a long time.186
More recently, combinatorial antibody libraries have been
made for primary amide hydrolysis.187
V. OTHER USES OF SUPPORTED
REAGENTS
The problems in the use of chlorine and chlorine compounds
for the disinfection of water were discussed in Chap. 3. One
problem is the residual toxicity of chlorine to nontarget or-
ganisms, as in cooling tower effluents. Using ozone as an al-
ternate involves a very toxic material, but does eliminate the
residual toxicity problem. The use of antibacterial polymers
is being investigated as an alternative way of disinfecting
water and air. Several are shown (5.39 through 5.42).
A silane containing hydroxyl and quaternary ammo-
nium salt groups was treated with a triisocyanate to prepare
a biocidal film that was active against Escherichia coli for
as long as 1 month.188 Cellulose was treated with the ap-
propriate trimethoxysilane to attach a phosphonium salt.189
Polyphosphonium salts based on polystyrene have been
prepared with spacers of varying lengths between the aro-
matic ring and the phosphorus atom.190 Polymeric
dichlorohydantoins were used to disinfect potable water
5.38b
5.39
Solid Catalysts and Reagents 121

5.40
5.43

Phase-transfer catalysts are used to facilitate reactions

between reagents that are in two different phases (e.g., 1-
bromooctane in toluene with aqueous potassium iodide to
form 1-iodooctane). They are usually quaternary ammo-
nium or phosphonium salts or crown ethers. They can com-
plicate the workup of the reaction and may be difficult to
recover for reuse. When they are insoluble polymeric ones,
workup and recycle can be done by simple filtration.192
The process is called triphase catalysis. In favorable cases,
their activity can be comparable with that of their lower
molecular weight analogues. They are often based on
5.41 cross-linked polystyrene, for which spacers between the
aromatic ring and the quaternary onium salt can increase
activity two- to fourfold. Copolymerization of 4-vinylben-
zyl chloride with styrene or N,N-dimethylacrylamide, fol-
lowed by treatment with tri-n-butylphosphine produced
catalysts that were used in the reaction of benzyl chloride
with solid potassium acetate (5.43).193
Increasing the density of the phosphonium salt in-
creased the rate of reaction of potassium iodide with 1-bro-
mooctane in a silica-supported catalyst (5.44).194 The cata-
lyst made from silica with 100-Å pores was ten times as
active as that from 60-Å–pore silica. When used in toluene,
the catalyst could be reused four times with no loss in
5.42 activity.
A polymeric formamide was a catalyst for the reaction
of alkyl bromides with potassium thiocyanate, even though

and air. Less than 1 ppm of free chlorine was released into
the water.191 The bromine analogue had even higher activ-
ity. A macroreticular copolymer made from divinylben-
zene and epithiopropyl methacrylate was treated first with
triethylenetetramine, then complexed with silver ion to a
polymer with high antibacterial activity. No silver ion dis-
solves in the water. There is no loss in activity after the
polymer is reused several times. Such polymers may prove
to be effective alternatives to the use of added chemicals to
sterilize water and air. They could be used in films,
columns, or other equipment. 5.44
122
5.45
the corresponding formamide was inactive. The catalyst
was made by copolymerizing styrene and divinylbenzene
with 4 mol% of the monomer shown in 5.45:195
Presumably, the polymer works because of a multiplic-
ity of functional groups that behave as weak ligands in the
proper conformation. Further experiments of this type with
other functional groups that might behave as ligands for in-
organic salts should be tried. Perhaps, combinatorial chem-
istry can be applied here.
Supports can sometimes be used to prevent the loss of ex-
pensive or toxic reagents or catalysts. Cinchona alkaloids
are used in the enantioselective dihydroxylation of olefins
with osmium tetroxide. Although the amount used may be
low on a mole percent basis, it is an appreciable amount on
a weight basis. One cannot afford to discard it. Terpolymers
were prepared from an alkaloid derivative of 4-vinylben-
zoic acid, 2-hydroxylethyl methacrylate, and ethylene gly-
col dimethacrylate. These were used with osmium tetroxide
and N-methylmorpholine-N-oxide or potassium ferri-
cyanide in the dihydroxylation. Stilbene gave the desired
product with 95% enantiomeric excess and 70% yield, com-
pared with 97%ee for a homogeneous reaction.196 The poly-
mer with the poisonous osmium tetroxide complexed to it
was recovered by filtration. Further work is needed, because
the enantioselectivity with stilbene and other olefins tends
to be slightly lower than with the corresponding reactions in
solution. Poly(vinyl pyridine) has been used to support os-
mium tetroxide in the dihydroxylation of olefins with hy-
drogen peroxide.197 The yields with cyclooctene and trans-
4-octene were 99–100%. The polymeric complex could be
recycled several times, but was slowly oxidized. Use of an
inorganic support, such as a zeolite or heteropolymetallate,
would avoid the oxidation. The use of rhodium supported on
cross-linked poly(vinyl pyridine) for the hydroformylation
of propylene and 1-octene works well enough that it is said
to “have commercial potential.”198
A silver dichromate complex with poly(ethyleneimine)
has been used to oxidize benzyl alcohol in toluene to ben-
zaldehyde in 98% yield.199 The polymeric reagent could be
regenerated several times with no loss in activity. No
Chapter 5
5.46
chromium was lost in the reaction. Polypropylene fabric
with vinylpyridine graft polymerized on to it has also been
used to support dichromate in the oxidation of alcohols.200
Less than 1 ppm of chromium was in solution after the re-
action. This is one method of avoiding the loss of toxic
heavy metal ions. There may be losses in mining the
chromium ore and converting it to dichromate. A better
method, as mentioned in Chap. 4, would be to select an in-
soluble catalyst that can be used in an oxidation with air.
Even so, proof of the ability to recycle a catalyst repeatedly
must show that no leaching occurs. A chromium aluminum
phosphate molecular sieve catalyst used in the oxidation of
-pinene to verbenone by a hydroperoxide was active in
reuse, but the filtrate was also able to catalyze the oxida-
tion.201 (This reaction was described in Chap. 4. For more
on zeolite and molecular sieve catalysts, see Chap. 6.)
Polymeric ligands can offer advantages in the separation
of metal ions. A copolymer of 4-vinylpyridine and divinyl-
benzene (5.46) separates iron(III) quantitatively.202 A poly-
meric hydroxamic acid favors iron(III) over other ions.203
Sherrington and coworkers have used polybenzimida-
zoles and polymides to complex metal ion catalysts and
thus avoid or minimize losses of the metal ions, some of
which are expensive. The first has been used to complex
palladium(II) for the Wacker reaction (5.47) of 1-octene
and 1-decene to ketones.204 (The other reagents for this re-
action are copper(II) chloride and oxygen.)
In some cases with 1-decene, the activity was higher
than the homogeneous counterpart. The catalyst was recy-
cled seven times. There was some loss of palladium at first,
but after about six cycles only 1 ppm was lost per cycle. No
hydrogen chloride needed to be added. No copper(II) chlo-
ride needed to be added after the first cycle. The catalyst
was used at 120°C and was stable to about 400°C. The sec-
ond polymer was used with molybdenum(VI) and tert-
butylhydroperoxide to convert cyclohexene to its epoxide
in quantitative yield.205 The catalyst was recycled nine
times with no detectable loss of molybdenum, but the ac-
tivity did decline. The polymeric ligand may favor site iso-
lation, whereas some other polymeric ligands allow forma-
tion of unwanted oxygen-bridged bimetallic species. The
third polymer was used to complex palladium(II) for the
Wacker reaction of 1-octene.206 Both nitrile groups proba-
bly coordinate to the palladium. The material was used for
six cycles. There was significant leaching in the first cycle,
Solid Catalysts and Reagents
5.47
but none in later cycles. The challenge is to devise active
supported catalysts that lose no metal and no activity on re-
peated use. This could allow their use in packed bed
columns. The strategy of Sherrington and co-workers ap-
pears to be to use supporting polymers that contain biden-
tate or tridentate ligand groups to hold the metal ion more
tightly. To be active, the metal ion must be coordinately un-
saturated. This means that the multidentate ligand must
leave an open site on the metal ion, or allow one or more
bonding groups to be displaced by the incoming reactants.
All excess metal ion must be washed out of the supported
catalyst before use, or it may appear to come out in the first
use. Deactivation mechanisms deserve further study.
Lower loading might favor site isolation and decrease any
loss of activity owing to reactions that produce inactive
binuclear species. If loss of activity is due to a buildup of
tarry side products that tend to block pores, a new more se-
5.49
123
5.48
lective catalyst may be needed or these by-products might
be extracted in a regeneration step. Sometimes, ultrasonica-
tion can do this during the reaction and prolong catalyst life.
A palladium derivative of an oligo-p-phenylenetereph-
thamide performed better as a catalyst for the reduction of
phenylacetylene to ethylbenzene than palladium on carbon
or silica or alumina catalysts.207 A rhodium(I) complex of
the polyamide (5.48) was used to catalyze the addition of
silanes to 1,3-dienes with good regio- and stereoselectiv-
ity.208 Rhodium is one of the metals that is so expensive
that losses must be kept at an absolute minimum.
This polyamide was also used to support a palladium
catalyst for the selective reduction of alkynes and di-
enes.209 Phenylacetylene was reduced to styrene in 100%
yield and 100% conversion. The reduction of 1-octyne was
80% selective to 1-octene at 100% conversion. There was
no loss in activity or selectivity after 11 successive runs. A
polymeric analogue of triphenylphosphine (5.49) has been
used to immobilize rhodium dicarbonylacetylacetonate for
the hydroformylation of 1-octene to the corresponding
aldehyde (5.50).210
The linear/branched ratio was 7.5:1, which was greater
than that found with the control catalyst in solution.
Rhodium(III) chloride has been immobilized on a support
made by polymerization of vinylpyridine and divinylben-
zene in the presence of silica. The best activity for the con-
version of methanol to acetic acid by carbon monoxide was
obtained after 20% of the pyridine groups were quaternized
with methyl iodide. This suggests ionic bonding of a tetra-
halorhodate ion to the polymer.211
Frequently, supported catalysts show lower activity
than homogeneous catalysts because of low loading.
124
5.50
5.51
Leaching of the metal may be a problem if the complex is
not strong enough. A polymer from the bipyridine
monomer 5.51 has also been used to complex rhodium
compounds.212 These polymeric complexes should be
more stable than those prepared from poly(vinyl pyridine).
Bergbreiter and co-workers have circumvented this
problem of lower activity by complexing the rhodium salt
on to poly(alkene oxide) oligomers (5.7) containing
diphenylphosphine groups.213
(C H ) PCH CH (OCH CH)
59(OCH2CH2)15
6 5 2 2 2
|
2
(5.7)
CH3
OCH2CH2P(C6H5)2  1.5 RhCl
The compound was used as a catalyst for the hydrogenation
of olefins. No rhodium was lost. This type of polymer
shows inverse temperature solubility. When the tempera-
ture was raised, the polymeric catalyst separated from so-
lution for easy recovery and reuse. This type of “smart” cat-
alyst will separate from solution if the reaction is too
exothermic. The catalytic activity ceases until the reaction
cools down and the catalyst redissolves. Poly(N-isopropy-
lacrylamide) also shows inverse temperature solubility in
water. By varying the polymers and copolymers used, the
temperature of phase separation could be varied (e.g., from
25 to 80°C).214 A terpolymer of 2-isopropenylan-
thraquinone, N-isopropylacrylamide, and acrylamide has
been used in the preparation of hydrogen peroxide instead
of 2-ethylanthraquinone.215 The polymer separates from
solution when the temperature exceeds 33°C to allow re-
Chapter 5
covery of the hydrogen peroxide. Because some an-
thraquinone is always lost to oxidation in such processes, a
better system would be to use an insoluble metal compound
that could form a M-OO-M that could be reduced with hy-
drogen to hydrogen peroxide. Such inverse solubility is
thought to be due to the release of water from the hydrated
forms of the polymers to give the anhydrous forms. This
method is used to isolate hydroxypropylcellulose in its
commercial preparation.
Efforts to heterogenize homogeneous enantioselective
oxidation catalysts often give lower enantioselectivity.
This may at least partly be due to the polymer not being
able to achieve the proper conformation for the metal
chelate catalyst with the substrate. Sometimes, insertion
of a spacer group between the polymer and the chelate
can help achieve the right conformation. By studying var-
ious supports, it has been possible to achieve 92% ee in
the oxidation of 1-phenylcyclohexene to its epoxide in
72% yield, using an amine oxide–peracid combination.
(This is the Jacobsen oxidation.) Thus, results comparable
with those using monomolecular analogues can be ob-
tained, combined with ease of separation for reuse.216
(Other enantioselective reactions are described in chap.
10.) One of the porous styrene-based resins used is shown
(5.52):
The desire to convert benzene directly to phenol with
30% hydrogen peroxide was mentioned in Chap. 4. A poly-
mer-supported salicylimine vanadyl complex (1 mol%)
was used to catalyze this reaction. Phenol was obtained in
100% yield at 30% conversion.217 There was no leaching
of the metal. The catalyst was recycled ten times after
which it started to break up. Oxidation of ligands is often a
problem with oxidation catalysts. Inorganic supports not
subject to such oxidation need to be tried to extend the life
of such catalytic agents.
The Swern oxidation of alcohols to aldehydes is carried
out with dimethyl sulfoxide. A polymeric version (5.53)
used poly(hexylene sulfoxide), obtained by the oxidation
of the corresponding sulfide with hydrogen peroxide to fa-
cilitate recovery and reuse, at the same time the bad smell
of dimethyl sulfide was avoided. Quantitative yields were
Solid Catalysts and Reagents
5.52
5.53
obtained with 1-octanol and 6-undecanol.218 However, it
would be better to use a process that does not produce
waste salts and that does not use methylene chloride in the
workup.
A polymeric protecting group was used in a synthesis of
pyridoxine by the Diels–Alder reaction (5.54).219
5.54
125
It is possible to put mutually incompatible reagents in
the same flask if each is on a separate resin. The reactions
in 5.55 could be run in sequential fashion or simultaneously
in cyclohexane. The reagent in the first step was poly
(vinylpyridinium dichromate), in the second, a perbromide
on a strongly basic resin (Amberlyst A26), and in the third,
126 Chapter 5

5.55

4-chloro-3-hydroxy-1-methyl-5-(trifluoromethyl) pyra- molecule needs to fit in. - and

-cyclodextrins form such
zole on another strongly basic resin (Amberlite inclusion compounds with polypropylene glycols with
IRA900).220 molecular weights up to 1000.225 The guests have reduced
volatility and enhanced stability to heat, light, and oxygen.
Liquid drugs can be converted to solids that are not hygro-
VI. CYCLODEXTRINS
scopic. Taste and odor problems can be overcome. Two
substances that might react with one another can be pack-
Cyclodextrins are included here as water-soluble supports.
aged together if one of them is isolated in a cyclodextrin.
They will also be mentioned in Chap. 7 on separations and
These hosts can also be used to separate molecules based on
in Chap. 8 on running reactions in water instead of organic
their size and shape. The bitter flavors in citrus juices,
solvents. Cyclodextrins221 are made by the enzymatic mod-
naringen, and limonin, can be separated in this way. Cy-
ification of starch.222 They are made commercially by Cer-
clodextrins form insoluble complexes with cholesterol in
estar and Wacker Chemie. They have conical structures of
foods. -Cyclodextrin prevents the enzymatic browning of
six, seven, and eight glucose units in rings, denoted - -,
apple juice by picking up the phenols present before en-
and
-cyclodextrin, respectively. Mercian Corporation has
zymes can act on them.226 At a ratio of two -cyclodextrin
a process for -cyclodextrin, which is more selective than
to one linoleic acid (but not at a 1:1 ratio), oxidation by
usual, that produces no - and only a small amount of the
lipoxygenase is reduced.227

-product.223 The insides are apolar and hydrophobic,

The ability to stabilize is also part of green chemistry,
whereas the outsides are hydrophilic (Table 5.2).
for, if things last longer, there will be less need to replace
All are 7.9–8.0 in height. A wide variety of guests can
them, and overall consumption will go down. Perpropionic
fit into these hosts, both in solution and in the solid state.
acid can be stabilized by -cyclodextrin so that 97% re-
These include paraffins, alcohols, carboxylic acids, noble
mains after 50 days at room temperature.228 Without the cy-
gases, and some polymers.224 Sometimes, only part of the
clodextrin 5% decomposes in just 11 days. The material
may be useful for bleaching and disinfection. Some artifi-
cial food colors are of questionable toxicity. Some have al-
Table 5.2 Properties of -, -, and
-Cyclodextrans ready been removed from the market. Natural colors offer
alternatives, but often lack the necessary resistance to heat
Solubility and low pH. If cyclodextrins can stabilize colors, such as
Diameter (A)
Cyclodextran in water the red in beet juice, there might be no further need for the
type MW (g/100 mL) Cavity Outside artificial colors.
Cyclodextrins can be used as “reaction vessels.” Chlori-
 972 14.5 4.7–5.2 14.6
nation, bromination,229 carboxylation,230 azo coupling, and
1135 1.85 6.0–6.4 15.4
others, favor the para-isomers over the meta- and ortho-

1295 23.2 7.5–8.3 17.5
isomers, when the compound being treated is inside a cy-
Solid Catalysts and Reagents
5.56
5.57
clodextrin. Pericyclic reactions, such as the Diels–Alder re-
action, are facilitated when done in cyclodextrins. A typi-
cal carboxylation used to make a monomer for a high-melt-
ing polyester is shown in Reaction 5.56:
The dicarboxylic acid was obtained in 65% yield with
79% selectivity. Fortunately, there are better ways (see
Chap. 6) to make this compound without the use of toxic
carbon tetrachloride. This method gives 100% selectivity at
71% conversion in the reaction of biphenyl-4-carboxylic
acid to form the 4,4-biphenyldicarboxylic acid. -Cy-
clodextrin accelerates the platinum-catalyzed addition of
triethoxysilane to styrene.231 The reaction is 100% com-
plete in 30 min at 50°C with the cyclodextrin, but only 45%
complete without it. The Wacker reaction of 1-decene pro-
duces several ketones owing to double-bond isomerization.
If the reaction is run in a dimethylcyclodextrin, isomeriza-
tion is reduced by faster reoxidation of palladium(O).232
The product 2-decanone is obtained with 98–99% selectiv-
ity (5.57).
No organic solvent is needed; no chloride is needed.
This is an important improvement because the chloride re-
quired in the usual Wacker reaction produces unwanted
5.58
127
corrosion. A bis(imidazoylmethyl)- -cyclodextrin (5.58)
converts a messy aldehyde cyclization, which gives a mix-
ture of products, to a clean reaction.233
Polymerization of phenyl or cyclohexyl methacrylate in
2,6-dimethyl- -cyclodextrin in water using a potassium
persulfate–potassium bisulfite initiator gave better yields
and higher molecular weights than obtained with an azo
initiator in tetrahydrofuran.234
Many derivatives of cyclodextrins have been prepared.
These include amines, hydroxylamines, hydrazines, ethers,
and others.235 A dimeric -cyclodextrin sulfide (5.59)
binds cholesterol 200–300 times as tightly as -cyclodex-
trin itself.236
A polymer was made by treating methyl -cyclodextrin
first then with hexamethylenediisocyanate, then with 2-hy-
droxyethyl methacrylate, followed by polymerization with
an azo initiator in the presence of cholesterol (i.e., molecu-
larly imprinted with cholesterol). After extraction of the
cholesterol, it was 30–45 times more effective in picking
up cholesterol than -cyclodextrin.237 Many others have
been prepared as “artificial enzymes” or enzyme mim-
ics.238 Some of these are chelating agents (5.60) that bind
128
REFERENCES
5.59
5.60
metal ions more strongly than the underivatized
cyclodextrin.
Cyclodextrins have also been immobilized on silica. -
Cyclodextrin has also been incorporated into a water-solu-
ble copolymer with a molecular weight of 373,000
(5.61).239
Presumably, other maleic anhydride copolymers could
be modified in the same way. A -cyclodextrin polymer
cross-linked with epichlorohydrin scavenged di(2-ethyl-
hexyl)phthalate from water with an equilibrium constant of
928. It could be used again after extraction of the phthalate
wih aqueous methanol.240
Larger analogues of cyclodextrins are known. A cyclic
decasaccharide of rhamnose with a 130-Å hole is
known.241
5.61
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204. (a) D.C. Sherrington and H.G. Tang, Macromol Symp
1994, 80, 193; (b) H.G. Tang and D.C. Sherrington, J Mol
Catal 1994, 94, 7; (c) G. Olason and D.C. Sherrington,
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205. M.M. Miller and D.C. Sherrington, J Catal 1995, 152, 368,
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207. F. Arena, G. Cum, R. Gallo, and A. Parmaliana, J Mol
Catal A Chem., 1996, 110, 235.
208. Z.M. Michalska, B. Ostaszewski, and K. Strzelec, J
Organomet Chem., 1995, 496, 19.
209. Z.M. Michalska, B. Ostaszewski, J. Zientarska, and J.W.
Sobczak, J Mol Chem. A Chem., 1998, 129, 207.
210. E. Bonaplata, H. Ding, B.E. Hanson, and J.E. McGrath,
Polymer, 1995, 36, 3035.
211. D. Jiang, X. Li, and E. Wang, Macromol Symp. 1996, 105,
161.
212. J.H. van Esch, M.A.M. Hoffmann, and R.J.M. Nolte, J Org
Chem., 1995, 60, 1599.
213. D.E. Bergbreiter, V.M. Mariagnaman, and L. Zhang, Adv.
Mater 1995, 7(1), 69; Macromol Symp., 1996, 105, 9.
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Chapter 5
away, Macromolecules, 1998, 31, 6053; (b) D.J. Gravert,
A. Datta, P. Wentworth, Jr., and K.D. Janda, J Am Chem.,
Soc., 1998, 120, 9481.
215. J.E. Guillet, K.C. Kohler, and G. Friedman, U.S. patent
5,624,543 1997.
216. (a) L. Canali, E. Cowan, H. Deleuze, C.L. Gibson, and
D.C. Sherrington, Chem. Commun., 1998, 2561; (b) X–D.
Du and X–D. Yu, J Polym Sci., Polym Chem., 1997, 35,
3249; (c) M.D. Angelino and P.E. Laibinis, Macro-
molecules, 1998, 31, 7581.
217. S.K. Das, A. Kumar, Jr., S. Nandrajog, and A. Kumar,
Tetrahedron Lett., 1995, 36, 7909.
218. T. Oyama, J. Ozaki, and Y. Chujo, Polym. Bull., 1997, 38,
379.
219. H. Ritter and R. Sperber, Macromolecules, 1994, 27, 5919.
220. J.J. Parlow, Tetrahedron Lett., 1995, 36, 1395.
221. (a) J. Szejtli, Cyclodextrin Technology, Kluwer Academic,
Dordrecht, Netherlands, 1988; (b) J.K. Poudrier, Todays
Chemist at Work, 1995, 4(2), 25; (c) W.J. Shieh and A.R.
Hedges, J Macromol Sci. Pure Appl Chem., 1996, A33,
673; (d) G. Wenz, Angew Chem. Int Ed Engl 1994, 33, 803;
(e) E. Weber, Kirk–Othmer Encyclopedia of Chemical
Technology 4th ed., 1995, 14, 129–131; (f) J.L. Atwood,
Ullmann’s Encyclopedia of Industrial Chemistry. 1989,
A14, 119; (g) V.T. D’Souza and K.B. Lipowitz, eds. Chem.
Rev., 1998, 98, 1741–2045; (h) M. McCoy, Chem. Eng.
News, Mar. 1, 1999, 25; (i) J–M. Lehn, ed., Comprehensive
Supramolecular Chemistry, vol. 3, Pergamon, Oxford,
1996; (j) M.M. Conn and J. Rebek, Jr., Chem. Rev. 1997,
97, 1647; (k) K.A. Connors, Chem. Rev 1997, 97, 1325.
222. T–J. Kim, B–C. Kim. and H–S. Lee, Enzyme Microb.
Technol., 1995, 17, 1057.
223. T. Kamiya, Chem. Eng., 1998, 105(8), 44.
224. (a) L. Huang and A.E. Tonelli, J Macromol Sci., Rev.
Macromol Chem., 1998, C38, 781; (b) A. Harada, Adv
Polym Sci., 1997, 133, 141; (c) G. Wenz, M.B. Steinbrunn,
and R. Landfester, Tetrahedron, 1997, 53, 15575.
225. A. Harada, Macromolecules, 1995, 28, 8406.
226. K. Hicks, R.M. Haines, C.B.S. Tong, G.M. Sapers, Y.
El–Atawy, P.L. Irwin and P.A. Seib, J Agric Food Chem
1996, 44, 2591.
227. (a) W.A. Reichenbach and D.B. Min, J Am Oil Chem.
Soc., 1997, 74, 1329; (b) J.M. Lopez–Nicolas, R. Bru, and
F. Garcia–Carmona, J Agri Food Chem., 1997, 45, 1144.
228. M. Granger, M. Dupont, and H. Ledon, U.S. patent
5,382,571 1995.
229. P. Velusamy, K. Pitchumani, and C. Srinivasan, Tetrahe-
dron, 1996, 52, 3487.
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Commun., 1995, 16, 31, 697; (b) H. Hirai, J Macromol Sci.
Pure Appl Chem., 1994, A31, 1491.
231. L.N. Lewis and C.A. Sumpter, J Mol Catal A Chem., 1996,
104, 293.
232. E. Monflier, E. Blouet, Y. Barbaux, and A. Mortreux.
Angew Chem Int Ed Engl 1994, 33, 2100.
233. R. Breslow, J. Desper, and Y. Huang, Tetrahedron Lett.,
1996, 37, 2541.
Solid Catalysts and Reagents
234. J. Jeromin and H. Ritter, Macromol Rapid Commun.,
1998, 19, 377.
235. (a) S. Hanessian, A. Benalil, and C. Laferriere, J Org
Chem, 1995, 60, 4786; (b) K.A. Martin, M.A. Mortellaro,
R.W. Sweger, L.E. Fikes, D.T. Winn, S. Clary, M.P. John-
son, and A.W. Czarnik, J Am Chem Soc, 1995, 117,
10443; (c) P.R. Ashton, R. Koniger, J.F. Stoddart, D.
Alker, and V.D. Harding, J Org Chem 1996, 61, 903.
236. R. Breslow and B. Zhang, J Am Chem Soc., 1996, 118, 8495.
237. (a) K. Sreenivasan, J Appl Polym Sci, 1998, 68, 1857,
1863; (b) H. Asanuma, M. Kakazu, M. Shibata, T. Hishiya,
and M. Komiyana. Chem. Commun., 1997, 1971.
238. (a) R. Breslow, Acc Chem Res 1995, 28, 146; (b) R. Bres-
low, S. Halfon, and B. Zhang, Tetrahedron, 1995, 51, 377;
(c) Y. Murakami, J–I. Kikuchi, Y. Hisaeda, and O.
Hayashida, Chem. Rev., 1996, 96, 721; (d) C.A. Haskard,
C.J. Easton, B.L. May, and S.F. Lincoln, Inorg Chem,
1996, 35, 1059; (e) Jiang and Lawrence, J Am Chem Soc.,
1995, 117, 1857.
239. M. Weickenmeier and G. Wenz, Macromol Rapid Com-
mun., 1996, 17, 731.
240. S. Murai, S. Imajo, Y. Takasu, K. Takahashi, and K. Ha-
tori, Environ. Sci. Technol., 1998, 32, 782.
241. G. Gattuso, S. Menzer, S.A. Nepogodiev, J.F. Stoddart, and
D.J. Williams, Angew Chem Int Ed Engl 1997, 36, 1451.
242. A. Chesney, Green Chem, 1999, 1, 209.
RECOMMENDED READING
1. D. Arntz. Catal Today 1993, 18, 173.
2. S. Borman. Chem Eng News Feb 12 1996, 29–54.
3. D.C. Sherrington. Chem Ind 1991, 1, 15.
4. J.K. Poudrier. Todays Chem Work 1995, 4(2), 25.
5. J.H. Clark, D.J. Macquarrie. Chem Soc Rev 1996, 25, 303.
135
EXERCISES
1. Compare the sizes of the cavities of cyclodextrins
with those of natural food colors, such as that of
beets, to see if shelf-stable food colors could be
produced using any of the cyclodextrins.
2. How could you immobilize a crown ether for re-
covery of a metal ion?
3. How might combinatorial chemistry be applied to
optimizing ligands for catalysts?
4. How many times should a supported catalyst be
reused to be sure that none is being lost and that
the activity remains high?
5. Design an ion-exchange resin that can be used at
200°C.
6. Would it be better to put an oxidation catalyst on
an organic or an inorganic support?
7. Compare the environmental effects of supported
toxic metal oxidants with oxidations performed
with hydrogen peroxide or oxygen.
8. Should each home be outfitted with a sterilizing
filter for incoming water instead of chlorination at
a central plant?
9. How would you put a shell of alumina or a transi-
tion metal oxide on a particle of magnetic iron ox-
ide? (If you are puzzled, see P. lengo, M. DiSerio,
A. Sorrentino, V. Solinas, E. Santacesaria. Appl
Catal A 1998, 167, 85.)
10. Why do so few students and faculty in university
chemistry departments use supported reagents and
catalysts?
6
Solid Acids and Bases
I. INTRODUCTION
This chapter continues the discussion of the use of solid
reagents to minimize exposure to hazardous reagents, to
make workups easier, and to minimize waste. Liquid acids
are also corrosive, may be difficult to recycle for repeated
use, and may show low activity or selectivity in some reac-
tions.1 Large amounts of sulfuric acid and hydrogen fluo-
ride are used in petroleum refining for the alkylation of
isobutane with olefins to produce high-octane gasoline.2 A
typical reaction of this type (6.1) is shown.
Hydrogen fluoride (bp 19.5°C) is more potent biologi-
cally than other Bronsted acids3 and could be a real prob-
lem if it were released into the environment.4 Olah has de-
vised a way to lower its volatility by the addition of a
tertiary amine.5 One refinery is using this method. Another
company has patented a method for using far less hydrogen
6.1
6.2
137
fluoride.6 Mobil used 1300 ppm of a 2:1 hydrogen fluo-
ride / boron trifluoride catalyst in the foregoing reaction.
The 2-butene conversion was 100%. The ratio of desired
trimethylpentane to dimethylhexane was 35:1. However,
the 22:1 ratio of isobutane to 2-butene must be reduced to
12:1 or lower to be useful in a refinery.7 A preliminary an-
nouncement by Hydrocarbon Technologies describes a be-
nign solid superacid catalyst for the reaction that appears to
be stable under normal-operating conditions in a continu-
ous-flow laboratory system.8 If this passes operation in the
pilot plant, it could answer the problem. However, several
other solid catalysts for the reaction have undergone rapid
deactivation in use.
Hydrogen fluoride is also used in the alkylation of ben-
zene with linear olefins to produce detergent alkylate for
sulfonation to produce detergents. This acid is now being
replaced in some plants by fluorided silica–alumina cata-
lysts in the U.O.P.–Petresa process.9 This type of catalyst
may be applicable to the alkylation of isobutane with
butenes.
The Hoechst–Celanese three-step process for the prepa-
ration of ibuprofen has replaced an older six-step process.10
Although the new process produces much less waste, hy-
drogen fluoride is used as both solvent and catalyst in the
acylation step (6.2).
138 Chapter 6

Table 6.1. Comparison of Acid Strengths by their Hos which ones to use. The various types of solid acids and
bases will be discussed in the following. Some soluble cat-
H0 alysts that have advantages over the current ones will also
HF-SbF5(1:1) 20 be included. Because many good reviews are available,
FSO3H-SbF5 (1:0.2) 20 only a few examples from the literature will be given to il-
sulfated ZrO2 16.0 lustrate the diversity of possibilities, the trends in current
SbF5/SiO2-Al2O3 13.8 research and the needs.
AlCl3-CuCl2 13.8
H3PW12O40 13.3
Cs2.5H0.5PW12O40 13.3 II. POLYMERIC SULFONIC ACIDS
Nafion 12.0
100% Sulfuric Acid 12.0 Sulfonic acid ion-exchange resins that can catalyze esteri-
fication, etherification, addition of alcohols and water to
olefins, were covered in Chap. 5. Degussa has made a
It should be possible to replace the dangerous hydrogen polysiloxane analogue with alkyl sulfonic acid groups on
fluoride with a solid acid in a solvent-free process. Two it.13 It is stable to 230°C, compared with 120°C for the
possibilities are the U.O.P.–Petresa catalyst and a high-sur- polystyrene-based ones.
face–area polymeric perfluorosulfonic acid.319 (These may duPont markets a polymeric perfluorinated sulfonic acid
require a film of liquid acid on the surface to prevent deac- as Nafion H (6.3). Dow sells a similar resin. The use of
tivation of the catalyst.) Nafion in electrolytic cells for the production of chlorine to
Many types of solid acid and base catalysts are known.11 eliminate the use of mercury was mentioned in Chap. 4.
Superacids are those that are at least as strong as 100% sul- Nafion H has been used as an acid in many organic synthe-
furic acid.12 The acid strengths are measured using basic ses.14 It is the polymeric equivalent of trifluoromethanesul-
indicators and are assigned a Hammett acidity function, fonic acid (triflic acid). When used as a catalyst for the
H0 Table 6.1 lists some superacids, with the strongest at pinacol rearrangement of 1,2-diols, dehydration was
the top. avoided.15 However, 1,4- and 1,5-diols did dehydrate with
Only the first and last are liquids. The stronger acids can it.16 It was also useful in an alkylation of aniline (6.4).17
catalyze some reactions that the weaker ones cannot (e.g., The reaction could not be carried out with the usual sul-
the alkylation of isobutane by 2-butene). As a rule of fonic acid ion-exchange resin, because its maximum use
thumb, it is probably better to use the weakest acid that will temperature was 120°C. The product cannot be made di-
do the job to avoid unwanted side reactions. Many solid rectly from acetone and aniline owing to the formation of a
acids, such as clays and molecular sieves, are shape- and dihydroquinoline by-product (from two molecules of ace-
size-selective, so that this also enters into the decision on tone and one of aniline). A shape-selective zeolite might al-
low the reaction to take place without formation of this by-
product. An inexpensive way of making this diamine from
acetone and aniline, similar to the preparation of bisphenol
A from acetone and phenol, could lead to new families of
polyamides, polyimides, polyureas, polyurethanes, and
epoxy resins. A palladium catalyst supported on Nafion
dimerized ethylene much faster in water than in organic
6.3 solvents. The butene was easy to separate.18

6.4
Solid Acids and Bases
6.5
The alkylation 6.5 was carried out by passing a solution
of the epoxide through a 10-cm column of Nafion H
powder:19 Although the yield was comparable with those
obtained with Sn(IV) chloride and with boron trifluoride
ethereate, it would be desirable to replace the CH2Cl2 /47
CFCl3 / 3 CF3CH2OH solvent used to swell the polymer
with one that is not toxic and not capable of destroying the
ozone layer.
The activity of Nafion as a catalyst has been increased
by applying it on silica by the sol–gel method using
tetramethoxysilane20 or tetraethoxysilane and dimethyl-
diethoxysilane.21 This increased its activity as a solid acid
catalyst up to 100 times that of bulk Nafion. It performed
better than Nafion on carbon in the dimerization of -
methylstyrene. It was a much better catalyst (seven times
on a weight basis) than Amberlyst 15, a typical sulfonic
acid ion-exchange resin. It was more active in the benzyla-
tion of benzene (6.6) than trifluoromethylsulfonic acid, a
reaction in which Amberlyst 15 and p-toluenesulfonic acid
were inactive.22
6.6
6.7
139
Hybrid membranes of zirconia in Nafion have been
made by the hydrolysis of zirconium tetrabutoxide by wa-
ter in the pores of a film.23
A Nafion–silica analogue, which was made by the
sol–gel method, gave over 99% conversion in the alkyla-
tion of benzene with 1-dodecene to make detergent alkylate
(6.7). It was also useful in acylations of aromatic com-
pounds.24
III. POLYMER-SUPPORTED LEWIS ACIDS
The use of inorganic supports for Bronsted and Lewis acids25
was described in Chap. 5. These included the metal chlorides,
as well as protonic acids, on inorganic supports that are sold
by Contract Chemicals as “Envirocats”26. They are air-stable,
nontoxic powders that can be reused several times.
Polypropylene containing hydroxyl groups has been
used with aluminum chloride and boron trifluoride to pre-
pare PPOAlCl2 and PPOBF2.27 These were used to poly-
140
merize isobutylene and vinyl isobutyl ether. They could be
reused for this purpose many times. A styrene–divinylben-
zene copolymer sulfonic acid was used with aluminum
chloride as a catalyst for the preparation of esters, such as
butyl lactate, in 99.5% yields.28 This may have involved
polymerSO3AlCl2. The protonic acid p-toluenesulfonic
acid, has been used as its salt with poly(4-vinylpyridine) in
the hydrolysis of tetrahydropyranyl ethers (i.e. in the liber-
ation of alcohols that have been protected by reaction with
dihydropyran).29
IV. SULFATED ZIRCONIA
Sulfonated zirconia is the strongest solid acid known.30 It
can isomerize butanes and alkylate isobutane with cis-2-
butene. Not everyone considers it to be a superacid.31 It can
be made by treatment of zirconium dioxide (zirconia) with
sulfuric acid,32 or by sol–gel methods starting with zirco-
nium alkoxides.33 Sometimes, the gel is dried with super-
critical carbon dioxide in an effort to keep a large surface
area. There is also a debate about what the material actually
is. Infrared spectral studies of material prepared by pyroly-
sis of zirconium sulfate suggest disulfate and monosulfate
groups on the surface (6.8)34 Hydrogen sulfates and cyclic
sulfates may also be possible. Some authors feel that sul-
fated tetragonal, but not monoclinic, zirconia is active.35
When sulfur is lost on heating, the tetragonal to monoclinic
transition can occur. Others believe that the monoclinic
form is also active.36
The activity of sulfated zirconia can be enhanced by
adding platinum, iridium, rhodium, osmium, palladium,
iron, manganese, or yttrium.37 With a combination of iron
and manganese, the activity is increased 1000-fold,38 but it
decays rapidly.39 With platinum as a promoter, the increase
6.8
Chapter 6
in activity is not as great, but it does not decay. Both cata-
lysts have induction periods in the isomerization of butane.
It is thought that the promoters work by producing inter-
mediate butenes. Although the platinum one may act cat-
alytically, the iron–manganese one may act irreversibly, or
may be deactivated by by-products. The platinum may be
in Pt–O and Pt–Pt bonds.40 Platinum-modified sulfated zir-
conia with hydrogen showed constant 90–100% selectivity
in the isomerization of hexane to branched C6 com-
pounds.41 (This isomerization can also be performed with
99% selectivity using Pt H--zeolite.42) A new method for
isomerizing petroleum naphtha, to increase the octane
number, with platinum-modified sulfated zirconia is said to
be cheaper than using aluminum chloride and to offer in-
creased capacity over the conventional zeolite method.43
Because the sulfate in sulfated zirconia is subject to
losses when the catalyst is calcined and under reducing
conditions, other more stable oxyanions are being exam-
ined. Tungstated zirconia is being studied.44 A platinum-
promoted tungstated zirconia was less active than sulfated
zirconia.45 Molybdate has also been used (e.g., to produce
an esterification catalyst that gave 95% yields).46 Other ox-
ides have been sulfated, including titanium dioxide and
tin(IV) oxide.47 The sulfated titanium dioxide was active in
cracking cumene at 180°C, whereas a silica–alumina cata-
lyst was inactive at this temperature.
This is a very active research area. There is a good chance
that, with further understanding of just what these catalysts
are and how they work, one will be found for the commer-
cial alkylation of isobutane with olefins. At present, the re-
action must be run at subambient temperatures to avoid the
side reaction of dimerization of the olefin. Perhaps, the cat-
alyst being offered by Hydrocarbon Technologies is of this
type and will be suitable. Because sulfated zirconia contains
Solid Acids and Bases
6.9
both protonic and Lewis acid acidity,48 it is possible that
poisoning one type selectively would lead to improved life-
times and yields. Another possibility would be to replace
sulfuric acid with a sulfonic acid, such as triflic acid, to pro-
duce zirconium triflates on zirconia. This might require dif-
ferent promoter metal ions. The use of rare earth metal tri-
flates as Lewis acid catalysts is described in Sec. VI.
V. SUPPORTED METAL OXIDES
Tantalum oxide on silica, made by treatment of silica with
tantalum alkoxides, is a catalyst for the Beckman rearrange-
ment of cyclohexanone to caprolactam (6.9).49 The catalyst
lasted at least 10 h in operation. This process eliminates the
by-product ammonium sulfate from the present commercial
rearrangement in sulfuric acid. Caprolactam is polymerized
to produce nylon-6. Alkylations can also be performed with
iron oxide catalysts (6.10).50 Other alcohols, such as n-propyl
and n-butyl alcohols, also worked. Highly acidic catalysts can
also be obtained by supporting tungsten oxide on iron, tin,
and titanium oxides.51
Benzylation of benzene with benzyl chloride using a
CuFeO4 catalyst gave diphenylmethane in 81.5% yield.52
The catalyst was reused five times, with no loss in activity.
VI. RARE EARTH TRIFLATES
Many Lewis acids, such as metal halides, must be used in
the absence of water to avoid hydrolysis. Some reactions
6.10
141
require them in stoichiometric amounts. Rare earth and a
few other metal triflates are stable to water, alcohols, and
carboxylic acids. They can be used as water-tolerant acids
in catalytic amounts.53 Although they usually are not solid
catalysts, they are included here because they can be re-
cycled for reuse with no loss in activity. This consists of
adding water, extracting away the organic compound,
concentrating the aqueous phase to allow the salt to re-
crystallize, and drying the salt. The aqueous phase may
simply be evaporated and the residue dried to recover the
catalyst quantitatively. For example, this method was
used to recover the catalyst from esterification of alcohols
with acetic acid to give 95–99% yields of acetates.54 Al-
though not strictly a rare earth, scandium triflate is in-
cluded in this group.
However, a catalyst made by microencapsulating scan-
dium triflate in polystyrene was easy to recover and reuse
with no loss in activity by filtration. In the imino aldol re-
action (6.11), its activity was greater than that of the unen-
capsulated counterpart, maintaining activity (90% yields)
after seven cycles:55 (Many Lewis acids do not work well
in this reaction.)
Anisole can be acylated with acetic anhydride in 99%
yield (6.12). Yttterbium triflate can also be used. The yields
are low when there is no activating group in the ring. The
rate is accelerated by the addition of lithium perchlorate.56
Acylation of alcohols works well with 1 mole% of scan-
dium triflate as a catalyst (6.13).57 The less toxic toluene
has also been used as the solvent in such acylations. The
142 Chapter 6

6.11

6.12

6.13

6.14
Solid Acids and Bases
6.15
6.16
yields with 4-dimethylaminopyridine and tributylphos-
phine as catalysts were lower and the reaction times longer.
Scandium triflate also catalyzes carbonyl ene reactions
(6.14).58
Rare earth triflates can also be used in the reaction of
aldehydes with aromatic rings (6.15).59
The catalysts are stable to amines (6.16).60
They can also act as catalysts for some reactions that
are normally catalyzed by base (6.17).61 They are also
suitable for aldol, Diels–Alder, pinacol, and ring-opening
6.17
6.18
143
reactions. Yttrium triflate has been used as a catalyst
for the polymerization of tetrahydrofuran62 and dyspro-
sium triflate for the polymerization of vinyl isobutyl
ether.63
Hafnium triflate has also been used for acylation and
alkylation of aromatic compounds.64 It has also been used
in aromatic nitration in a process (6.18) that eliminates the
usual waste acid from such reactions.65 The products are in-
termediates in the synthesis of toluene diisocyanates used
in making polyurethanes. The catalyst could be reused with
144
6.19
little or no loss in activity or yield. (For more on iso-
cyanates, see Chap. 2.)
Scandium dodecyl sulfate has been used as a catalyst in
an aqueous dispersion (6.19).66 The reaction was 5000
times faster in water than in methylene chloride. It was also
slower in dimethyl sulfoxide, acetonitrile, ethyl ether,
tetrahydrofuran, and methanol.
Indium(III) chloride is another Lewis acid that is stable
in water. (For the use of indium(III) chloride without or-
ganic solvents, see Chap. 8.) It has been used as a catalyst
in Diels–Alder and other reactions, such as 6.20.67 After
the product is extracted with an organic solvent, the aque-
ous layer can be used to catalyze another reaction. It should
also be possible to just separate the organic layer without
the use of a solvent.
Tris(pentafluorophenyl)boron is an air-stable, water-
tolerant Lewis acid for aldol, Diels–Alder, and Michael re-
actions.68 It is effective at 2 mole% in some reactions. Its
recycle has not been demonstrated.
6.20
6.21
Chapter 6
VII. SOLID BASES
Potassium fluoride on alumina is a solid base.69 (It forms
potassium hydroxide by exchange of fluoride for hydroxyl
groups on the surface of the alumina.) An example of its
use is given by Reaction 6.21.70 It has also been used with-
out solvent in the Tishchenko reaction of benzaldehyde to
give benzyl benzoate if 94% yield.71 Potassium fluoride on
an aluminum phosphate molecular sieve was a weaker base
in the isomerization of 1-butene.72
Alkali and alkaline earth carbonates catalyzed the
Knoevenagel reaction (6.22) of benzaldehyde with
malononitrile.73
Layered double hydroxide carbonates of magnesium
and aluminum are called hydrotalcites (e.g., Mg6Al2(OH)16
CO3-H2O). They can be used as solid bases before or after
calcination to produce mixed magnesium–aluminum ox-
ides.74 They have been used to catalyze the addition of al-
cohols to acrylonitrile;75 the reduction of ketones with iso-
Solid Acids and Bases
6.22
propyl alcohol, with 92–95% selectivity (the Meerwein–
Ponndorff–Verley reduction);76 the reaction of glycerol
with glycerol trioleate to produce a monoglyceride;77 and
the aldol and Knoevenagel reactions, in 88–98% yields.78
When the aldol reaction was run at 0°C, the hydroxyketone
was obtained in 88–97% yields, with no dehydration to the
unsaturated ketone. The Meerwein Ponndorff–Verley re-
duction has also been run in the gas phase with aluminum-
free titanium -zeolite with 95% selectivity.79 A calcined
hydrotalcite has been used to alkylate aniline exclusively to
the monoalkyl derivative (6.23).80 Such selectivity is diffi-
cult to obtain by other methods. They have also been used
for the addition of trimethylsilyl cyanide to aldehydes and ke-
tones in up to 99% yield,81 and the condensation of aldehydes
with active methyl groups.82
Magnesium oxide, calcium oxide, and hydroxyapatite
[Ca10(PO4)6(OH)2] have been used to catalyze the opening
of epoxide rings by trimethylsilyl cyanide, with 92–99%
regioselectivity.83 This is higher than found in homoge-
neous systems. Trimethylsilyl cyanide is the synthetic
equivalent of toxic hydrogen cyanide. Intercalation of
cobalt phthalocyaninetetrasulfonate into a layered magne-
sium–aluminum double hydroxide increased its activity in
the air oxidation of 2,6-dimethylphenol by a factor of
6.23
6.24
145
125.84 Such layered double hydroxides can also serve as
hosts for guests, such as carboxylates, sulfates, phosphates,
porphyrins, and polyoxometallates that can be put in by
anion exchange.85
The ortho-alkylation of phenol (6.24) has been carried
out with a catalyst that was a solid solution of cerium(IV)
and magnesium oxides.86 At 32% conversion, the selectiv-
ity was 90% for o-cresol and 8.6% for 2,6-xylenol. [The
latter is a monomer for a poly(phenylene oxide), an engi-
neering plastic.] There was no decay of activity.
A silica-supported phenoxide gave a 99% yield in the
Michael reaction (6.25).87
VIII. ZEOLITES AND RELATED
MATERIALS
Zeolites are well known to chemical engineers for indus-
trial separations and as catalysts; the average chemist in an
organic chemical laboratory uses them only as molecular
sieves for drying solvents. They offer the promise of more
environmentally friendly catalysts that will improve selec-
tivity and reduce waste.88 Zeolites89 are inorganic alumi-
nosilicate polymers. They contain AlO4 and SiO4 tetrahe-
146 Chapter 6

6.25

dra, linked by shared oxygen atoms. No two aluminum

units are adjacent. For each aluminum, there must be an ad-
ditional cation, usually from an alkali or alkaline earth
metal, for electrical neutrality. There are about 50 natural
zeolites, with names such as chabazite, clinoptilolite, fauj-
asite, and mordenite. [Mineral names usually end in ite.] In
addition, many are synthetic.
The structures contain channels in one, two, or three di-
rections. When one channel intersects another, there may
be a larger cage. The channels contain the alkali or alkaline
earth metal cations (i.e., the exchangeable cations and wa-
ter). Diagram 6.2690 shows the channels of ZSM-5. Struc-
ture 6.2791 is in zeolites X and Y. Each corner represents a
silicon or aluminum atom. There is an oxygen atom on each
line between them. I and II indicate where cations might be.
After drying, some zeolites are about 50% voids. The
pore diameters in angstoms and percentage pore volumes for
several zeolites with sodium cations are shown in Table 6.2.
The pore diameter varies with the cation in it. Data for Figure 6.1 Pore dimensions (nm) of zeolites in comparison
zeolites A and X are shown in Table 6.3. with the diameters of hydrocarbons (Reprinted with permission
Figure 6.192 shows pore dimensions of Zeolites in com- from E.G. Derouane in M.S. Whittington and A.J. Jacobson,
parison with the diameters of hydrocarbons (in nm). The Eds., Intercalation Chemistry, Academic Press, 1982, p. 101.)
silicon to aluminum ratio also varies, with typical values
such as:
Zeolite A 1.0
X 1.1
Y 2.4
Silicalite Infinite (has no exchangeable cations)
Other zeolites may have ratios as high as 10–100.

6.27

6.26 & 6.27 Reprinted with permission from V. Ramamurthy,

D.F. Eaton and J.V. Caspar, Acc. Chem. Res., 1992, 25, 299.
6.26 Copyright 1992 American Chemical Society.
Solid Acids and Bases
Table 6.2 Comparison of Pore Diameters and Pore Volumes
Characteristic 4A X Y
Pore Diameter 4.1 7.4
Pore volume (%) 47 50
Table 6.3 Variation in Pore Diameter as a Function of Its
Cation
Cation Zeolite Diameter (A)
Zeolite A
Calcium exchanged 5A 4.2–4.4
Sodium exchanged 4A 3.6–4.0
Potassium exchanged 3A 3.3
Zeolite X
Sodium exchanged 13X 7.4
Calcium exchanged 7.8
The names of zeolites are confusing and relatively un-
informative. Workers in the field keep an atlas of zeo-
lites93 nearby, but the ordinary chemical laboratory prob-
ably will not have one. These materials have been named
in a variety of ways, but the most common involves the
place where the material was first made. ZSM-5 means
zeolite SOCONY–Mobil No. 5; SOCONY reflects the
origin of the company as Standard Oil of New York.
Newer materials from the same place are designated
MCM, with a number following, which means Mobil
Composition of Matter. VPI-5 was made at Virginia Poly-
technic Institute and State University. The man who made
it is now at the California Institute of Technology where
he makes CIT zeolites. TS-1 (titanium silicalite) and tita-
nium- are titanium-containing molecular sieves. USY is
an ultrastable version of zeolite Y. For those who do not
work in the field all of the time, it would be desirable to
have a more informative system. It would be an improve-
ment if each paper mentioning a zeolite would define it
the first time the name is given. This could include the
relative amounts of the elements present, whether it con-
tains one-, two-, or three-dimensional channels, the pore
size in angstroms (Å), and the number of oxygen atoms in
the major channel window. A sample might be
(10:1:0.25-Si:Al:Na, 3-D, 4.0 Å, 10 O atoms). If the in-
formation were available, the acidity or basicity could
also be mentioned as well as whether the acid sites were
Bronsted or Lewis acid.
Zeolites can be made by formation of a gel from sodium
aluminate, sodium silicate, and sodium hydroxide in the
147
Synthetic
mordenite ZSM-5
7.4 6.7–7 6
48 28 —
presence of a template, usually a quaternary ammonium
hydroxide, followed by a digestion in which the material
crystallizes (Eq. 6.1).94 [This is sol–gel technology.95]
NaAlO2  Na2SiO3  NaOH (Eq. 6.1)
100°C/6 h
 R4NOH → gel → zeolite
A wide variety of quaternary ammonium salts have been
used in an effort to prepare new zeolitic structures.96
Molecular modeling can sometimes help in the design of
new structures.97 Combinatorial synthesis has been per-
formed using a 100-well Teflon block.98 Tetrapropylam-
monium hydroxide has been used to make titanium sili-
calite (TS-1).99 Tetrabutylammonium hydroxide is used to
prepare ZSM-11. Hexadecyltrimethylammonium chloride
has been used with tetramethylammonium silicate with
sodium aluminate and sodium hydroxide to prepare meso-
porous (pores larger than about 15 Å) zeolites.100 The di-
gestion was accomplished with microwave radiation in 1
min at 160°C, to give MCM-41. (Mobil’s MCM-41 series
has uniform pores that can be varied from 16 to 100 Å.101
One way to vary the pore size is to use mixtures of tem-
plates.102) The use of seed crystals can sometimes shorten
times in such microwave digestions.103 Application of
a magnetic field during the preparation of MCM-41 pro-
duced aligned pores.104 The syntheses are sometimes
modified by inclusion of alkyltrialkoxysilanes, which may
contain a variety of functional groups, such as methacry-
oyl, vinyl, mercaptan, amine, or other, to alter the hy-
drophobicity and reactivity of the final product.105 Al-
though most templates are burned out, some can be
recovered for reuse by extraction with supercritical carbon
dioxide.106 A tetraethylammonium fluoride template was
removed with aqueous acetic acid.107 Removal of the tem-
plate with ozone at 250°C gave a more uniform pore-size
distribution.108 A tin silicate analogue was made from
tin(IV) chloride, hexadecyltrimethylammonium chloride,
tetramethylammonium hydroxide, and tetramethylammo-
nium silicate.109
Although the reactions are usually run in water, ethylene
glycol, propyl alcohol, sulfolane, pyridine, and such, have
also been used.110 Occasionally when metal cations
are provided for charge compensation, it is possible to pre-
pare zeolites under nonbasic conditions. CoZSM-5 has
148
been prepared from a 0.25 HF/0.75 NaF/0.25 NaCl/1.25
(C3H7)4NBr/10 SiO2/330 H2O, plus (C2H5)4N22
CoCl42 mixture at 170°C.111 CuMCM-41 can be
made starting with a mixture of Si(OC2H5)4, C16H33
N(CH3)3Br, Cu(NH3)24 Cl2 2 , ethyl amine, and Al
Cl36H2O in water.112
Nonionic templates, such as amines, have also been
used.113 Mesoporous silica molecular sieves have been
made from n-dodecylamine, tetraethoxysilane, ethanol,
and water.114 After the product dried in the air, the template
was recovered by extraction with hot ethanol. Usually, the
template, which may occasionally be expensive, is burned
out. Large-cage zeolites have been made with diamines as
templates.115 The use of C12H25NHCH2CH2NH2 gave a
mesoporous sieve stable up to 1000°C, and to boiling wa-
ter for more than 150 h, which is much greater than that ob-
served with most mesoporous sieves.116 The mechanical
and hydrothermal stability of MCM-41 has been improved
by postsynthesis treatment with aluminum chloride hy-
drate.117 There was no change in the X-ray pattern after 16
h in boiling water. Previous AlMCM-41 became amor-
phous after boiling in water for 6 h.
Nonionic surfactants such C11H23–C15H31O(CH2
CH2O)nH, can be used in place of the amine.118 These can
also be used with alumina, titania, and zirconia. These sur-
factants are less expensive and less toxic than the amines,
and they are also biodegradable. Block copolymers of ethy-
lene oxide have also been used.119 A large-pore silica zeo-
lite has been prepared using bis(pentamethylcyclopentadi-
enyl)cobalt(III) hydroxide as a template.120 An EMT
zeolite has been made using 18-crown-6 as the template.121
Much larger voids (320–360 nm) have been made in alu-
mina, titanium dioxide, and zirconium oxide by use of the
sol–gel method with polystyrene latex spheres (which are
removed at the end of the synthesis).122
After the zeolite is made, it may be modified.123 Burn-
ing out the quaternary ammonium salt template leaves hy-
droxyl groups that are acidic. These can be neutralized with
a variety of ions. If the ion is cesium, the resulting zeolite
is basic.124 For zeolite X, the basicity is CsX  RbX  KX
 NaX. Various ions can be exchanged for sodium and
potassium and other ions in zeolites. Adding in some rare
earth ions can make the zeolite more stable.125 Aqueous ex-
change with copper(II) ions adds copper on two types of
sites. However, the copper can be added on only one type
of site selectively by using copper(II) hexafluoroacetylace-
tonate.126 The hydroxyl groups reacted with triiso-
propoxyaluminum to form a catalyst that was more active
in the reduction of ketones with isopropyl alcohol than was
triisopropoxyaluminum itself.127 Boron trifluoride etherate
was added to modify the acidity of the catalyst for
etherification.128
Chapter 6
Molybdenum sulfide clusters can be added with
Mo3S4 4 ion or by molybdenum carbonyl, followed by hy-
drogen sulfide.129 Palladium ion can be added, then re-
duced to palladium metal by isopropyl alcohol with ultra-
sound or by hydrogen.130 Its activity in the Heck reaction
was comparable with that of some of the best homogeneous
catalysts. Ruthenium clusters were formed inside zeolite X
by addition of the ruthenium ion, then reducing with hy-
drogen.131 Sodium clusters have been placed into zeolite Y
by dissolving sodium in the zeolite.132 These are inorganic
electrides. Some organic cations formed inside zeolites can
be stable for weeks.133 A ruthenium dinitrogen complex
made inside a zeolite was stable to 523 K.134
It is possible to form a complex in a supercage of a zeo-
lite by introducing the metal ion first, then the ligand. If the
complex is too large to enter the pore, it cannot escape, but
can be used for catalysis in place.135 This has been done in
zeolite Y with iron and manganese bipyridyl complexes.136
Such encapsulation can offer steric protection against oxi-
dation of the catalyst, giving longer life to oxidation cata-
lysts.137 It can also prevent the dimerization of ruthenium
and rhodium ions that occurs when they are oxidized in
solution.138
Removal of some aluminum is often desirable to stabi-
lize a zeolite. This can be done hydrothermally with steam,
or with tetrachlorosilane or ammonium hexafluorosili-
cate.139 Gaseous metal halides can be used to introduce alu-
minum, boron, gallium, and indium into the H or ammo-
nium form of a zeolite. To improve selectivity, the pore
openings can be narrowed by the chemical vapor deposi-
tion of silica from tetraethoxysilane.140 Pore size can also
be adjusted with tetrachlorosilane, titanium(IV) chloride,
and antimony pentachloride.141 Both pore size and activity
in HY zeolites have been modified by sequential treatment
with silane and NO.142 To utilize the size- and shape-selec-
tivity of zeolite catalysts in reactions, it may be necessary
to deactivate exterior acid sites. This can be done with
bulky amines, such as 4-methylquinoline, coking the cata-
lyst with mesitylene, introducing silicon polymers, and so
on. In one case, it was performed by grinding the zeolite
with barium acetate supported on silica in an agate mor-
tar.143 Tetrabutyl and tetraphenylgermanium have also
been used for this purpose.144
There are other microporous solids that are not alumi-
nosilicates; hence, they are not zeolites. The titanosili-
cates, such as titanium silicalite (TS-1), which are selec-
tive catalysts for oxidations, are discussed in Chap. 4.
Much work is going into extending these findings to ma-
terials with larger pores to accommodate larger substrates
for oxidation. Molecular sieves also include the aluminum
phosphate (AIPO) family.145 These have been modified
by inserting a variety of cations into them, including
Solid Acids and Bases
cobalt,146 magnesium,147 nickel,148 silicon,149 titanium,150
and vanadium.151 The MgAPO-5 preparation involved a
20-min digestion with microwaves or a conventional di-
gestion for 24 h.152 Methylphosphonic acid can also be
used in place of phosphoric acid.153 Cage compounds that
may serve as models for the aluminum phosphates have
been made by treatment of trimethylaluminum with tert-
butylphosphonic acid.154 A molecular sieve containing
zinc has been prepared from 2-aminoethylphosphonic
acid.155 Alkylenebisphosphonates have been used with
copper, zinc, and zirconium ions to prepare layered struc-
tures.156 Gallophosphate157 and cobalt gallophosphate158
have also been prepared. Mesoporous molecular sieves of
alumina have been prepared starting with aluminum sec-
butoxide, using nonionic surfactants as templates.159
Measuring the acidity of the Bronsted and Lewis acid
sites is problematic. The adsorption and desorption of var-
ious amines has been used, but there is some disagreement
about what it means.160 Some workers prefer to use iso-
propylamine, which desorbs only from Bronsted sites.
Solid-state nuclear magnetic resonance (NMR) has also
been used in the study of reactions on zeolites.161 Many ze-
olites crystallize into crystals that are too fine for conven-
tional X-ray analysis. A new method that uses synchrotron
X rays on microcrystalline powders promises to make it
much easier to determine the structures of zeolites and re-
lated materials.162
There are many uses of zeolites and molecular sieves,
based on their size and shape selectivity. As catalysts,
they offer less or no corrosion, little waste, ready adapta-
tion to continuous processes, high thermostability, and
other attributes.163 Their limitations include deactivation
owing to occasional plugging of pores with secondary
products, and the difficulty of using them with bulky
molecules. The first limitation can sometimes be over-
come with a continuous loop through the reactor, then
through a regeneration cycle. Zeolite catalysts for the
alkylation of isobutane with olefins in the preparation of
gasoline are said to work when fresh, but to deactivate
rapidly.164 Rorvik and co-workers preferred a hexagonal
faujasite (H-EMT) that they could regenerate with air.165
If this could be combined with the circulating fluidized
bed system of continuous regeneration, the process might
displace hydrogen fluoride and sulfuric acid in this
reaction in refineries. Alkylation of isobutane with
1-butene using zeolite NaY, zeolite H-USY, or sulfated
zirconia under supercritical conditions, with or without a
molar excess of carbon dioxide, did not have the pore
plugging problem.166 With further development, this
might replace the current liquid acid process. Ultrasound
should be applied during the reaction with solid acid
catalysts to see if it can keep the pores open without
149
the carbon dioxide. The propylene oxide oligomers that
can build up in the pores of titanium silicalite during
the oxidation of propylene with hydrogen peroxide can be
removed by heating with refluxing dilute hydrogen per-
oxide to reactivate the catalyst.167 The limitation on the
use of bulky molecules accounts for the tremendous
amount of work on mesoporous solids being done to-
day.168 In cases where delaminated zeolites can be used,
this limitation has been overcome.320
The largest commercial use of zeolites is probably in
detergents, for which they pick up the calcium and magne-
sium ions in hard water. They replace sodium tripolyphos-
phate, which caused eutrophication of water bodies. [Phos-
phorus is the limiting nutrient in many lakes and rivers.]
They are also used to separate linear from branched paraf-
fins (e.g., by calcium zeolite A); p-xylene from mixed
xylenes (e.g., by barium zeolite X); and 95% oxygen from
air (for use in steel-making and in wastewater treatment).169
This method of enriching oxygen uses less energy than the
conventional cryogenic distillation. Carbon dioxide, hydro-
gen sulfide, and mercaptans can be removed from gas
streams with zeolites. The catalytic cracking of petroleum is
done with zeolite X or Y, stabilized with rare earth cations.
Natural gas is converted first to methanol, then to gasoline
with ZSM-5 in New Zealand. Clinoptilolite is used to re-
move ammonium ion (another nutrient) from wastewater. A
few of the better examples of the use of zeolites as catalysts
for organic reactions will be given in the following.321
Chiba and Arco will use a zeolite in their alkylation of
benzene with ethylene to produce ethylbenzene for conver-
sion to styrene.170 The older process used aluminum chlo-
ride. The use of reactive distillation in this reaction can give
99.7% specificity at 100% conversion.171 The ethylene is
fed in at the bottom of the catalytic zone in the refluxing
benzene. The ethylbenzene goes to the distillation pot. Any
polyalkylated material is transalkylated later with benzene
with the same molecular sieve catalyst. Cumene can be
produced by the alkylation of benzene with propylene
(6.28) in a higher than 99% yield with -zeolite.172 The
catalyst gives a higher yield than the phosphoric acid on a
support that it replaces. By using the catalytic distillation
method mentioned for ethylbenzene, the yield of 99.95%
pure cumene is 99.6%, which is 5–6% higher than in a con-
ventional plant.173
The principle of removing a product as soon as it is
formed, and before any secondary reactions can occur, is
one that should be applied more widely to increase yields.
Benzene is also alkylated with 1-olefins (e.g., where R
is C10H21) to prepare “detergent alkylate” for sulfonation to
make detergents. A UOP/Petresa process, using a fluorided
silica–alumina catalyst, gave 92% linear alkylbenzene and
6% branched alkylbenzene at 97% conversion with a cata-
150
6.28
lyst life of 182 h.174 The catalyst could be regenerated by
washing first with a paraffin, then with an alcohol, then
drying. The cost of the process is 30% lower than one us-
ing hydrogen fluoride. Liang and co-workers used zeolite
HY, which tended to gum up and become deactivated.175
They overcame this problem by using a circulating flu-
idized bed in which the catalyst passed through the reactor
then through the regenerator. The system worked, and it
was easy to operate.
Zeolites are useful in favoring p-disubstituted benzene
products, which have smaller diameters than the other iso-
mers. The raw material for the terephthalic acid used in
making poly(ethylene terephthalate) is p-xylene. It has
been produced from n-pentane (6.29) using a MFI zeolite
catalyst.176
The significant finding was that the xylene fraction was
99% para. The other fractions are not lost. Toluene can be
disproportionated to p-xylene and benzene with H-ZSM-5
treated with a little hexamethyldisiloxane to give 99% p-
xylene, so that the usual separation of the ortho- and meta-
isomers with another zeolite would not be required.177 Ben-
zene can be transalkylated with the higher aromatics to give
toluene. Ethylbenzene can be isomerized to p-xylene.
Ethylbenzene can be alkylated with ethanol in the presence
of a modified ZSM-5 catalyst to produce p-diethylbenzene
with 97% selectivity.178
6.29
Chapter 6
Halogenation179 and benzoylation of subtituted ben-
zenes also favor the para-products. Nitration of toluene
with n-propyl nitrate in the presence of H-ZSM-5 gives
95% para-selectivity.180 Benzene can be nitrated with 65%
nitric acid in the vapor phase at 170°C over a mordenite
catalyst.181 (Most zeolites are not stable to protonic mineral
acids. Mordenite is an exception.) The nitration of aromatic
compounds can also be carried out with a sulfuric acid
on silica catalyst that is slurried in methylene chloride to
give 97–98% yields.182 The catalyst could be recovered
and reused with less than 3% loss in activity after three
runs. These methods eliminate the problem of what to do
with spent by-product sulfuric acid from conventional
nitrations.
The acetylation of alcohols and phenols with acetic an-
hydride and HSZ-360 zeolite at 60°C used no solvent. The
acetate of 1-dodecanol was obtained in 98% yield, and the
acetate from 1-naphthol in 100% yield.183 The acylation of
anisole with acetic anhydride at 100°C without solvent us-
ing zeolite H- gave 4-methoxyacetophenone (6.30) in
98% yield.184 The catalyst could be recovered, regenerated,
and reused with no decrease in yield. These reactions show
that not all zeolites are used at high temperatures in the va-
por phase.
Anisole has also been acylated with aliphatic or aro-
matic carboxylic acids, with 92–95.6% selectivity at
Solid Acids and Bases
6.30
6.31
70–87% conversions, using zeolite Y9 at 155°C.185 Acyla-
tion of benzene with acetic acid using H-ZSM-5 gave ace-
tophenone with 91% selectivity at 43% conversion.186 In
one case, the ortho-isomer (6.31) is favored, presumably
because the intramolecular cyclic transition state fits better
in the ZSM-5 zeolite than whatever transition state leads to
the para isomer.187 This is a Friess Rearrangement. The
para ratio was 98.7:1.3.
6.32
6.33
151
Naphthalene (6.32)188 and biphenyl (6.33)189 also alky-
late selectively.
Industrially important olefins can be made with the help
of molecular sieves. Methanol can be converted into 50%
ethylene and 30% propylene with a SAPO catalyst at
350–500°C.190 Isobutene can be made by isomerization of
n-butenes over clinoptilolite at 450°C with 91.6% selectiv-
ity at 23.5% conversion,191 or with H-ferrierite with 92%
152
6.34
selectivity.192 Zeolites with 8-membered rings are too
small, and 12-membered rings do not suppress char, but
10-membered ring zeolites let the isobutene out while sup-
pressing dimer and oligomer formation.193
Acetonitrile can be produced from ethanol, ammonia,
and oxygen in 99% yield using a SAPO catalyst at
350°C.194 It can be reduced to ethylamine with 98% selec-
tivity using a 1.1 Co/1.1 Ni/0.9 mg/1.0 Al layered double
hydroxide and hydrogen at 393 K.322 Methylamine and
dimethylamine are more valuable than trimethylamine.
When methanol and ammonia are reacted in a zeolite, such
as clinoptilolite, mordenite, or chabazite, the products are
largely the desired monomethyl and dimethylamines, one
of the best distributions being 73.1% mono-, 19.4% di-and
1.4% tri-, at 97.7% conversion.195 Alkylation of aniline
6.35
Chapter 6
with methanol over chromium phosphate produced the N-
methylaniline with 94–95% selectivity.196
Sometimes the choice of zeolite can determine which
product is obtained. This is true in the alkylation of 4-
methylimidazole with methanol (6.34) in the vapor
phase.197 The product from a Meerwein–Ponnodorff–Ver-
ley reduction (6.35) varied with the zeolite catalyst.198
High selectivity for acrolein, propylene, and allyl ether
from allyl alcohol (6.36) can be obtained by using different
zeolites.199 A combination of acid or base strength and cav-
ity size may be responsible for these effects.
Hydrogenation is selective for size and shape.200 Cyclo-
hexene, but not cyclododecene, was reduced by hydrogen
with a rhodium in NaY zeolite. The Beckmann rearrange-
ment of cyclohexanone oxime to caprolactam (6.37) (for
Solid Acids and Bases
6.36
polymerization to nylon 6) is usually done with sulfuric
acid, which ends up as low-value ammonium sulfate. No
ammonium sulfate is formed when zeolites or molecular
sieves are used. The rearrangement is 95% selective at
100% conversion with a ZSM-5 catalyst,201 93% selective
at 99% conversion with a B-MFI zeolite,202 and more than
98% selective at 68% conversion with H-Beta D.203 Sum-
itomo has worked out a commercial process.204
The conversion of tert-butanol to pivalic acid with H-
ZSM-5 (6.38) eliminates the usual sulfuric acid.205
MCM-41 has been used to replace sodium or potassium
hydroxide in the synthesis of jasminaldehyde (6.39). Se-
lectivity of 90% at more than 80% conversion was obtained
using a 1.5:1 ratio of benzaldehyde/1-heptanal and 5%
catalyst.206
6.37
6.38
6.39
153
Photochemical reactions of materials enclosed in zeo-
lites can lead to different proportions of products, or in
some cases, to different products than those run in solu-
tions.207 The distribution can vary with the zeolite. The en-
hanced selectivity in the oxidation of hydrocarbons with
oxygen208 was mentioned in Chap. 4. The oxidation of cy-
clohexane in NaY zeolite with oxygen and visible light to
yield cyclohexane hydroperoxide with complete selectivity
at more than 40% conversion may have considerable in-
dustrial potential. Heating the hydroperoxide yields only
cyclohexanone which can be oxidized to adipic acid for use
in making nylon 6,6.209
Photorearrangements of aryl esters in zeolites (6.40)
give different product distributions.210 Photosensitized ox-
idation of stilbene with oxygen (6.41) leads to different
products in solution and in a zeolite.211
Selective photoreduction of the double bond in steroidal
, -unsaturated ketones has been done with MCM-41 and
NaY in isopropyl alcohol/hexane (6.42).212 No reduction
occurs in the absence of the zeolite.
Clearly, photochemical reactions in zeolites offer inter-
esting possibilities in directing syntheses. Light is an envi-
ronmentally clean reagent. Scale-up of such reactions for
154
6.40
6.41
commercial use may require some innovative equipment.
There is also a question of quantum yields, for not all the
light may penetrate the zeolite. This will not be a problem
if sunlight can be used. Any photosensitizers that are re-
quired will need to be recycled and reused repeatedly.
Zeolites can also be used in polymerizations. Tetrahy-
drofuran has been polymerized in high yield by acetic an-
hydride in combination with a dealuminated zeolite Y to a
product with a narrow molecular weight distribution.213 H-
ZSM-5 also works in the presence of a trace of water.214
Acrylonitrile has been polymerized in the mesoporous ze-
olite MCM-41, using potassium persulfate as a catalyst,
then converted to graphite.215 Polymerization of methyl
methacrylate in MCM-41 with an azo initiator gave a poly-
mer with a number average molecular weight of 360,000
6.42
Chapter 6
and a polydispersity of 1.7, compared with a control with-
out the zeolite of 36,000 and 2.8.216 The limited space in
the zeolite hindered bimolecular termination.
Zeolites and molecular sieves may be useful in places
where organic materials would not stand up. Mordenite can
be used to concentrate the sulfur dioxide in flue gas.217 The
higher concentration in the concentrate makes recovery by
conversion to sulfuric acid easier. A silver–sodium zeolite
A molecular sieve can be used to recover mercury from gas
streams to prevent destruction of aluminum heat exchang-
ers by mercury.218 A synthetic dealuminized zeolite can
pick up mercury and dioxins from incinerator flue gas
without picking up sulfur dioxide.219 It lasts for 3 years. In-
organic ion exchangers can be used with radioactive mate-
rials that cause the usual organic ion-exchange resins to de-
Solid Acids and Bases 155

teriorate. Doped titanates can remove cesium and strontium
preferentially over sodium, calcium, barium, and magne-
sium ions.220
It is now possible to prepare defect-free zeolite mem-
branes for use in separations.221 (More details on separa-
tions can be found in Chap. 7.) A mordenite membrane on
a porous alumina support had a separation factor for ben-
zene over p-xylene of more than 160.222 A ZSM-5 mem-
brane on porous alumina separated n-butane over isobutane
by a factor of 31 at 185°C.223 The next step is to use them
in membrane reactors to separate products as they form.
In summary, zeolites and molecular sieves are versatile
solid acids and bases that can be tailored to provide selec-
tivity in reactions by size and shape. After estimating the
sizes of the starting materials, products, and transition
state, a series of sieves approximating the required sizes
and acidity or basicity can be tested.224 After finding one
that works, it can be optimized by selective deactivation of
unwanted sites, narrowing of the pore openings, if neces-
sary, and stabilization by dealumination or addition of sta-
bilizing ions. If deactivation in use is a problem, methods
of regeneration will need to be studied.
IX. CLAYS
Clays are layered, hydrated silicates of aluminum, iron, and
magnesium.225 Most are crystalline inorganic polymers,
but a few are amorphous. They consist of tetrahedral and
octahedral layers as shown in Fig. 6.2.
The tetrahedral layers contain silicon and oxygen, but
sometimes with some substitution of silicon by aluminum
or iron. The octahedral layers are mainly aluminum,
iron(III), iron(II), or magnesium ions. The spaces between
the layers contain water and any cations necessary to main-
tain electrical neutrality. The water can be taken out
reversibly by heating. Montmorillonite (in the smectite
family) has two tetrahedral layers for each octahedral one.
Its overall formula is [Al1.67Mg0.33(Na0.33)]Si4O10(OH)2.

Figure 6.2 Diagrammatic representation of the succession of layers in some layer lattice silicates (12) where  is oxygen;  ,

hydroxyl; •, silicon; , Si–Al; , aluminum;  Al–Mg; , potassium; •, Na–Ca. Sample layers are designated as O, octahedral; T,





tetrahedral; and B/G, brucite or gibbsitelike. The distance (in nm) depicted by arrows between repeating layers are 0.72, kaolinite; 1.01,
halloysite (10 A); 1.00, mica; ca 1.5, montmorillonite; and 1.41, chlorite. T. Dombrowski, Kirk-Othmer Encyclo. Chem. Technol. 4th
Ed., 1993, 6, 381– . Copyright 1993 John Wiley & Sons. Reprinted by permission of John Wiley & Sons.
156
This is one of the more common clays used for the cataly-
sis of organic reactions.
The layers in the smectites can be expanded by interca-
lation with water, alcohols, ethylene glycol, glycerol, and
such. (For reviews on intercalation into layered lattices see
O’Hare226 and Oriakhi.227) The initial spacing between
layers of 12–14 Å increases to 17 Å when the clay is inter-
calated with ethylene glycol. If the structure is heated to
550°C, the structure collapses to a 10 Å spacing. The
swelling of sodium montmorillonite with water has been
modeled.228 The collapse of the structure on heating to high
temperatures has been a problem in some catalyses, be-
cause the surface area and, hence, the catalytic activity de-
crease greatly. To avoid this problem, the clay layers can be
propped open. Smectites can be pillared with oxides of alu-
minum, zirconium, titanium, cerium, iron, or other such, to
give 30 Å between layers. In the most common case,
an aluminum hydroxy cluster cation [(Al13O4(OH)24
(H2O)12]7 is inserted by cation exchange, then heated to
form the oxide pillars. The spaces between layers in mont-
morillonite pillared with iron are 76 Å.229 Even with pillar-
ing, many clays are not very stable to thermal and hy-
drothermal treatments, which detracts from their use as
catalysts. A “highly stable” clay has been made by pillar-
ing with Al2(OH)3Cl.230 One pillared with Ce(III)/Al was
stable to steam at 800°C.231
Clays have many uses.232 These include making bricks,
chinaware, filled paper, filled plastics, drilling muds, and
so on. The use of clay in paint can make it thixotropic (i.e.,
the paint is thick until pushed with the brush, whereupon it
becomes temporarily thinner.) This is due to the plate-like
structures of clays. Attapulgite can be used in brake linings
for cars and trucks as a replacement for carcinogenic as-
bestos. Kaolin can be heated to 600°C to form molecular
sieves. The cation-exchange capacity of clays is essential
to the mineral nutrition of plants. Putting 4% clay into ny-
lon 6 raised the heat distortion temperature 50°C. and in-
creased the tensile strength with no loss in impact
strength.233 Putting 5% of exfoliated clay into poly(ethy-
lene terephthalate) raised the heat distortion temperature
6.43
Chapter 6
20–50°C and increased both the modulus and crystalliza-
tion rate three fold.234 (Slow crystallization of this polymer
leads to uneconomically long cycle times in molding.)
Similar techniques have used to add clays into polyethy-
lene,235 polypropylene,236 and epoxy resins.237
Cationic and anionic clays have been used as catalysts in
many organic reactions, including electrophilic aromatic
substitutions, addition and elimination reactions of olefins,
cyclizations, isomerizations, rearrangements, and such.238
As catalysts for the Friedel–Crafts reaction they offer sev-
eral advantages over aluminum chloride and other typical
Lewis acids. They are easy to handle, noncorrosive, and
low in cost. Yields and conversions are high with reduced
times and catalyst levels. Compared with some reactions
that require stoichiometric amounts of the Lewis acid, zinc
chloride on K10 montmorillonite can be used at a level
2000 times lower. Polyalkylation and rearrangements are
often absent. They are regenerable. No toxic waste is pro-
duced. The acidity can be modified easily by varying the
cation and any anions on it.
Alcohols, phenols, thiols, and amines can be acetylated
with acetic anhydride in the presence of montmorillonite
K10 under mild conditions.239 Octyl acetate was obtained
in 1 hr from 1-octanol, in 96% yield, using K10 at room
temperature. Peracetylation of sugars, such as glucose, has
been done in similar fashion in 92–99% yields.240
Alcohols were used to alkylate aromatic compounds in
90–95% yields with K10 montmorillonite, but the cationic
intermediate isomerized so that several isomers were ob-
tained with different points of chain attachment.241 Ultra-
sound accelerated the benzylation (6.43) of aromatic com-
pounds (where X  Cl and R  H or Cl).242
Nonpoisonous and nonhydrolyzable neodymium chlo-
ride has been used on clay for the same reaction, giving
80% selectivity where X  Cl and R  H.243 There was no
loss in activity after 5000 turnovers. Zinc chloride on K10
montmorillonite can also be used with reagents in the va-
por phase (6.44).244
Experiments with the same catalyst in solution gave
3–50% yields. The use of boron trifluoride can be avoided
Solid Acids and Bases
6.44
6.45
by oligomerizing 1-decene to oils in 81% conversion using
K10 montmorillonite.245
Reactions on clay catalysts show some selectivity by
size and shape. Aluminum montmorillonite was used to re-
arrange phenyl ethers (6.45).246 The bulkier tert-butyl
group led to only the para product. Allylation of aromatic
compounds with octenols (6.46) gave only the unbranched
isomer.247 Aniline can be ethylated with ethanol to give
86% N-ethylaniline and 14% N,N-diethylaniline in 52%
conversion with K10 montmorillonite with, or without,
vanadium oxide at 400°C.248
6.46
6.47
157
Copper nitrate on montmorillonite (Claycop) has been
used with acetic anhydride to nitrate chlorobenzene in 100%
yield, giving 13:85 ortho/para isomers.249 When an iron ox-
ide pillared clay was used, 94% para-isomer was obtained.250
Claycop and its iron analogue have been used to oxidize a
pyrazoline to a pyrazole (6.47) in 64–97% yields.251
Kaolin was used as a catalyst for the preparation of
thioketals from ketones in 90–95% yields.252 Thioketals
have been hydrolyzed in 91–100% yields using a mixture
of finely ground Fe(NO3)39H2O and K10 montmorillonite
in hexane.253 Microwaves have been used to accelerate the
158
6.48
6.49
reaction of ortho-phenylenediamine with carboxylic acids
(6.48) over K10 montmorillonite.254 Microwaves have
given better conversions in the reaction of imidazole with
ethyl acrylate (6.49) than thermal activation.255
Selectivity in the dehydration of olefins is improved
with pillared clays. Clays with aluminum oxide or mixed
aluminum and iron oxide pillars converted isopropyl al-
cohol to propylene with more than 90% selectivity.256 A
small amount of isopropyl ether was formed. When zeo-
lite Y is used, the two products are formed in roughly
equal amounts. A tantalum-pillared montmorillonite con-
verted 1-butanol to butenes at 500°C with 100% selec-
tivity at 41% conversion.257 The product contained a
17:20:16 mixture of 1-butene/cis-2-butene/trans-2-
butene. No butyraldehyde or butyl ether was formed. A
pillared clay has been used for the alkylation of benzene
with 1-dodecene without formation of dialkylated prod-
ucts.258 The carbonylation of styrene proceeded in 100%
yield (6.50).259
A pillared clay containing a quaternary ammonium bro-
mide surfactant has been used as an inexpensive phase-
transfer catalyst for the reaction of alkyl halides with
sodium azide to form alkyl azides in 82–93% yields.260 It
could be reused at least twice, with little or no loss in yield.
6.50
Chapter 6
Clays have also been pillared with polyoxometalate
ions, such [(PW11VO40)4].261 Other layered materials can
also be pillared. Zirconium phosphate has been pillared
with chromium(III) oxide.262 A layered titanate has been
pillared with silica.263 The need for a separate pillaring step
has been avoided in the preparation of some porous lamel-
lar silicas which are structurally similar to pillared clays.264
Eight to twelve carbon diamines were used with tetra-
ethoxysilane in ethanol with added water to make them in
18 h at room temperature. The template was recovered by
solvent extraction before the silica was calcined.
A self-supporting film of montmorillonite was prepared in
aqueous phosphoric acid, which immobilizes the clay by
cross-linking.265 The film remained intact in hot water and
retained its ion-exchange capacity. Such films offer the po-
tential of separating mixtures. Pillared layered structures may
be able to separate flat molecules from others. They may also
be able to separate more highly branched structures from lin-
ear molecules. The first step is to estimate the sizes of the
molecules in the mixture relative to the interlayer distances
and the density of pillars. These properties of the membrane
can be varied. Vegetable oils have to be winterized by crys-
tallizing out the saturated triglycerides. Biodiesel fuel, which
consists of methyl oleate from transesterification of rapeseed
Solid Acids and Bases
oil with methanol, must be winterized by crystallizing out the
methyl stearate, so that the fuel can be used in cold weather.
The proper pillared, layered solids might permit passage of
the saturated esters, but not the unsaturated ones. The process
might also be used to remove the cholesterol-raising satu-
rated fats from food oils. Separation of 2,6-diisopropylnaph-
thalene from its 2,7-isomer should also be tried. There should
also be some reactions of flat molecules that could be more
selective if run with a catalyst in a pillared clay. There is great
interest in mesoporous analogues of titanium silicalite for se-
lective oxidation of larger molecules. A layered silicate pil-
lared with titania should be tried in such oxidations. Clays
pillared with polyoxometalates, containing vanadium,
molybdenum, or tungsten, should also be tried in oxidations.
X. HETEROPOLYACIDS
Heteropolyacids266 that may be useful catalysts are primar-
ily of the Keggin ([XnM12O40](8-n)) and Dawson
([X2M18O62]6) types. In the Keggin ions, X can be P5,
As5, B3, Si4, or Ge4, and M can be Mo, V, or W,
where more than one valence state is possible. For the
Dawson ions, X can be P5 and As5 with M as for the
Keggin ions. The structure of the (PW12O40)3 ion is
shown diagrammatically (6.51):
6.51
Reprinted with permission from M. Misono, Catal. Rev.-Sci.
Eng., 1987, 29, 269. “Heterogeneous Catalysis by Heteropoly
Compounds of Molybdenum and Tungsten,” figure 1. Copyright
1987 Marcel Dekker.
159
The central heteroatom in the more or less spherical
structure is surrounded by metal oxide tetrahedra. The mate-
rials are strong acids. Both Bronsted and Lewis acid acidity
are present. Various ligands, such as methylpyridines, can
coordinate with them.267 Because the complex with ethyl
ether is insoluble in ethyl ether, this can be used as a method
of isolation. Transition metals, such as Mn(III), in the poly-
oxometalate ion can be oxidized or reduced without de-
stroying the polyoxometalate.268 Heteropolymetalates can
serve as ligands for transition metal ions.269 As an example,
cyclopentadienyltitanium has been inserted in this way.270
The heteropolyacids are very soluble in water. They can
form sparingly soluble or insoluble salts with ions such as
ammonium, cerium, cesium, potassium, silver, and such.
The acids are often soluble in organic solvents, such as al-
cohols, ketones, carboxylic acids, and carboxylic esters.
Long-chain tetraalkylammonium salts can also be soluble
in organic solvents. In a sense, heteropolyacids are soluble
versions of insoluble metal oxide catalysts. They can be
used as catalysts both in solution and as solids. A catalyst
that is soluble in water would be a solid if used alone or in
a hydrocarbon medium. They can also be placed on insol-
uble supports. In the insoluble forms at least, they offer the
advantages of easy separation and recovery for reuse.
Heteropolyacids can be prepared (Eq. 6.2) in aqueous
solutions at pH 1–2.
12 Na2MoO4  Na2SiO3
 26 HCl→ H4SiMo12O40 (Eq. 6.2)
 26 NaCl  11 H2O
Salts may be obtained by careful neutralization with an al-
kali carbonate. Although the heteropolyacids are stable in
acidic aqueous solutions, they tend to decompose in alkaline
aqueous solutions. The resistance to hydrolysis varies as Si 
Ge  P  As, and W  Mo  V. The acids are relatively sta-
ble thermally, the decomposition temperatures following the
order H3PW12O40 (610°C)  H4SiW12O40 (540°C) 
H3PMo12O40 (495°C)  H4SiMo12O40 (375°C). Ammonium
and cesium salts of heteropolyacids can sometimes have or-
ganized microporous structures.271 The salts of Dawson acids
and 1,6-diaminohexane are also microporous.272 It is unclear
whether or not these organized microporous structures depart
from the generalized globular structure shown on 6.51.
Heteropolyacids have been used as catalysts in a variety
of acid-catalyzed and oxidation reactions.273 A few exam-
ples will be given to show the advantages of these catalysts.
Showa Denko will use a heteropolyacid catalyst in a new
plant that it is building for the addition of acetic acid to ethy-
lene to produce ethyl acetate.274 Butyl acrylate can be made
with 96% selectivity at 98% conversion in a flow system us-
ing H3PW12O40 on carbon.275 The activity of immobilized
160
6.52
dodecatungstosilicic acid on carbon in vapor-phase esterifi-
cation is higher than that of the zeolite and ion-exchange
resins now used by industry.276 In the esterification of ethyl
alcohol with acetic acid with Cs2.5H0.5PW12O40 silica, the
turnover frequency based on the acid sites present was
higher than those with Amberlyst 15 (a sulfonic acid ion-ex-
change resin) and H-ZSM-5 (an acidic zeolite).277 When the
esterification of pyridine-2,6-dicarboxylic acid with 1-bu-
tanol was carried out homogeneously with H3PW12O40, the
diester was obtained in 100% yield.278 When the heteroge-
neous catalyst Ce0.87H0.4PW12O40 was used, the activity
was lower, but the catalyst could be recovered and reused.
In view of the activity of scandium and rare earth triflates as
acids, discussed earlier, further work should be done with
scandium and rare earth salts of heteropolyacids, varying
both the elements used and the stoichiometry.
The alkylation of isobutane with butene at room tem-
perature with Cs2.5H0.5PW12O40 gave the desired eight-car-
bon fraction in 79% yield, with 73% selectivity plus 14%
butene dimers.279 This catalyst was much more active than
sulfated zirconia. The catalyst was resistant to moist air, at
least for a few minutes. At 80°C and 73% conversion of
butene, 67.5% of the product contained eight-carbon
atoms, with 21% in the C5–C7 range and 11.5% C9 or
larger.280 As mentioned at the beginning of this chapter,
this reaction is now carried out on a large scale with
hydrogen fluoride and sulfuric acid in the preparation of
gasoline. This is a promising lead. Further work is needed
to reduce the level of dimerization. It will also have to
6.53
Chapter 6
be shown that this catalyst does not deactivate in the reac-
tion over a long time period, or that it can be reactivated
readily.
tert-Butyl methyl ether is a common gasoline additive
that raises the octane number and reduces air pollution
from cars. It can be made with nearly 100% selectivity at
71% conversion using H3PW12O40 at 85°C.281
H4GeW12O40282 and H3PW12O40283 are also effective cata-
lysts. In current manufacturing, Amberlyst 15 (a sulfonic
acid ion-exchange resin) has the disadvantages of thermal
instability and loss of acid sites by leaching. Alkylation of
p-xylene with isobutylene using H3PW12O40 (6.52) yields
the monoalkylated product with 75% selectivity (90% con-
version).284 With a sulfuric acid catalyst, the selectivity is
only 7%.
Dihydromyrcene was hydrated in aqueous acetic acid
with 90% selectivity (to dihydromyrcenol and its acetate)
at 21% conversion with H3PW12O40 (6.53) without the
isomerization and cyclization that often accompany such
reactions.285 This catalyst was much more active that sul-
furic acid and Amberlyst 15 (a sulfonic acid ion-exchange
resin).
The amount of cesium can determine the pore size in a
microporous heteropolyacid salt. The pore size is Cs2.5 
Cs2.2  Cs2.1 in CsnH3-nPW12O40 with the best activity
for larger substrates in the first.286 Reaction 6.54 could be
carried out with the first, but not with the other two. Typi-
cal microporous zeolites, zeolite Y and H-ZSM-5, were
inactive.
Solid Acids and Bases
6.54
Heteropolyacids can be very useful in oxidation reac-
tions. In contrast with metal chelate catalysts that usually
become oxidized and deactivated eventually, the het-
eropolyacids are extremely stable to oxidation. Acetalde-
hyde is produced commercially from ethylene by the
Wacker reaction with a palladium(II) chloride catalyst,
copper(II) chloride, oxygen, and water. The corrosive con-
ditions are a disadvantage of the process. Catalytica Inc.
has devised a process (6.55) that uses only 1% as much pal-
ladium and chloride as the usual process. It uses a small
amount of palladium(II) chloride with a partial sodium salt
of phosphomolybdovanadic acid.287
The same reaction (R  H) was run to 80% conversion
in 50 h with palladium(II) chloride and a manganese phos-
phomolybdovanadate on silica.288 Palladium(II) sulfate
was used with a phosphomolybdovanadic acid to convert
1-butene (R  C2H5) to 2-butanone with more than 95%
selectivity at 98% conversion.289 Cyclohexene was con-
verted to cyclohexanone with 97% selectivity using
Pd(NO3)2 /CuSO4 /H3PMo12O40 /O2 in 1 h at 80°C.290 Pal-
ladium(II) sulfate and copper(II) sulfate have been used
with a phosphomolybdovanadic acid and a per(2,6-di-O-
methyl) -cyclodextrin in an aqueous system to convert 1-
6.55
6.56
161
decene (R  C8H17) to 2-decanone with 98% selectivity at
100% conversion.291 The cyclodextrin derivative was used
as an inverse phase-transfer catalyst to take the olefin into
the aqueous phase where it could react with the catalyst.
The reaction has also been combined with a further oxida-
tion to convert ethylene directly to acetic acid in 94%
yield292 using a combination of palladium and tellurium
salts with magnesium silicotungstate on a silica support. A
commercial plant is being built to run this reaction by this
or a similar catalyst.293
Butane has been isomerized to isobutane in 95% yield
(at 24.5% conversion) with platinum/Cs2.5H0.5PW12O40 at
200–300°C. under hydrogen at 0.05 atm.294 The hydrogen
reduced deactivation of the catalyst. The oxidation of
isobutane to isobutylene is needed for the synthesis of tert-
butyl methyl ether to put into gasoline. Isobutylene, in turn,
can be oxidized to methacrylic acid for conversion to
methyl methacrylate, an important monomer (6.56). Mak-
ing methyl methacrylate this way avoids the use of toxic
hydrogen cyanide in the present commercial process.
The oxidative dehydrogenation of isobutane to isobuty-
lene has been carried out with a salt of a Dawson acid,
K7P2W17MnO61, with 79% selectivity to isobutylene, 3%
162
to propylene, and 18% to carbon monoxide and carbon
dioxide.295 Methacrolein has been oxidized to methacrylic
acid with 87% selectivity at 84% conversion using a het-
eropolyacid salt made with molybdenum, arsenic, copper,
phosphorus, vanadium, and cesium compounds.296 Isobu-
tane can be oxidized directly to methacrylic acid using
Cs2.5Ni0.08H0.34PVMo11O40 and oxygen at 320°C, but with
only 36% selectivity, much carbon monoxide and dioxide
are formed at the same time.297 Further work is needed to
improve the yields in these reactions.
Heteropolyacids can be used as catalysts in oxidations
with hydrogen peroxide, tert-butyl hydroperoxide, or oth-
ers. Hydrogen peroxide was used with [(C6H13)4N]
[(PO4){WO(O2)2}4] to convert 1-nonene to its epoxide in
93–94% yield.298 This system converted cyclooctene to
its epoxide in 99% yield. The conversion of 1-octene to
the corresponding epoxide took place with 95% selectiv-
ity at more than 85% conversion using hydrogen peroxide
with H3PW12O40 and a quaternary ammonium salt, such
as hexadecylpyridinium chloride as a phase-transfer
agent.299 Unfortunately, the chlorinated solvents that were
necessary for the reaction gradually decomposed the cata-
lyst. An insoluble catalyst for this reaction that required
no organic solvent was made by the sol–gel method (Eq.
6.3).300
Si(OC2H5)4  C6H5Si(OC2H5)3
 (R )3Si(CH2)nN(C8H17)(CH3)2 Cl
H 0
→
2
support (Eq. 6.3)
polyoxometalate  pulp that is now said to be cost-competitive.307 The process
↓ involves two steps; first anaerobic delignification of the
catalyst
Cyclooctene was converted to its epoxide (80% conver-
sion) with hydrogen peroxide using this catalyst.
Oxidation of cyclohexane with hydrogen peroxide and a
SiW10[Fe(H2O)]2O386 catalyst at 83°C for 96 h gave a
55:45 cyclohexanol/cyclohexanone mixture in 66% con-
version with 95% utilization of hydrogen peroxide.301 If
the time can be reduced and cheap hydrogen peroxide is
available, this could replace the current relatively ineffi-
cient air oxidation of cyclohexane in the production of
nylon.
Sulfides have been converted to the corresponding
sulfoxides with tert-butyl hydroperoxide in 95–99% se-
lectivity using a H5PV2Mo10O40 on a carbon catalyst.302
Combinatorial synthesis of polyoxometallates identified
one with a PVW ratio of 1:2:10 that was used to oxidize
tetrahydrothiophene to its sulfoxide at 95°C with 95% se-
lectivity.303 Oxidation of dibenzothiophene with hydrogen
peroxide in the presence of phosphotungstic acid pro-
Chapter 6
duces the corresponding sulfone in nearly 100% yield.304
The sulfone can then be removed on silica. This process
can be used to remove sulfur from petroleum, leaving
only 0.005% in the oil. The sulfone could be burned off
the silica and the sulfur dioxide converted to elemental
sulfur in a Claus unit. Such a process is needed to
make low-sulfur gasoline and diesel fuel to reduce air
pollution.
Neumann and co-workers have used sandwich-type
polyoxometalates as catalysts for such reactions.305 The
sandwich consists of transition metal ions between two
Keggin anions, as in K12WZnMn(II)2(ZnW9O34)2. In some
cases, quaternary ammonium salts were used as the cations
to take the catalyst into organic solvents. Sulfides were ox-
idized to sulfoxides with 30% aqueous hydrogen peroxide
in 85–90% yields, with some sulfone also being formed.
The system was more than 99% selective in the conversion
of cyclooctene to its epoxide. The system also shows good
selectivity between double bonds (6.57), probably the re-
sult of the bulky anion and the increased electron density in
alkyl-substituted double bonds.
This type of catalyst has also been used with ozone to
oxidize cyclohexane to cyclohexanone with more than
98% selectivity at 41% conversion.306 This appears to be
an even better route to replace the current commercial oxi-
dation of cyclohexane than that in reaction above that used
hydrogen peroxide. Because ozone is toxic, care will be
needed to contain it.
Polyoxometalates, such as K5SiVW11O40, are used in an
environmentally-benign bleaching process for kraft wood
pulp; second, an aerobic oxidation of the organic waste
in the bleaching liquor to carbon dioxide and water. The re-
covery of the polyoxometalate for reuse is 99.99%. No
chlorine or organic solvents are used. Oxygen is the termi-
nal oxidant. This process can be used in an effluent-free
mill.
Heteropolyacid catalysts are also sometimes used with
light. Ethanol has been dehydrogenated by H4SiW12O40
with light to acetaldehyde and hydrogen with 100% selec-
tivity.308 Photocatalysis is also useful in removing low con-
centrations of organic pollutants from wastewater.309
Chlorophenols in water were photolyzed in water with oxy-
gen and H3PW12O40, with 97% removal in 120 min. The
commonly used titanium dioxide gave 77% removal under
these conditions. This could be a very practical process if it
can be performed with a supported catalyst in sunlight.
Several ways have been used to place finely dispersed
heteropolyacids on supports. Polyaniline has been used as
a support for H4SiW12O40.310 Heteropolyacids have been
placed on silica,311 in mesoporous zeolites,312 and even
Solid Acids and Bases
6.57
in a viral particle from which the RNA had been re-
moved.313 A polyoxometalate catalyst became more active
and selective as an oxidation catalyst when it was sup-
ported on a silica that contained polyethyleneoxy chains
[i.e., SiO (CH2CH2O)nCH2CH2OCH3].314 Reuse was not
mentioned. The carbon chain might oxidize gradually dur-
ing use, in contrast with catalysts without carbon atoms.
Heteropolyacids have also been embedded in polyethersul-
fone and poly(phenylene oxide) to increase their activ-
ity.315 H3PMo12O40 dispersed in a polyethersulfone had ten
times the activity in the oxidation of ethanol to acetalde-
hyde by oxygen as the bulk heteropolyacid.316 K8SiW11O39
was reacted with a trichlorosilyl-terminated poly(dimethyl-
siloxane) to anchor the polyoxometalate to the polymer.317
The use of polyoxometalates to pillar clays was mentioned
earlier.
Finally, antiviral activity has been found in some poly-
oxometalates, such as K7PTi2W10O407H2O against human
immunodeficiency virus (HIV).318
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Solid Acids and Bases 173

314. R. Neumann and M. Cohen, Angew, Chem. Int. Ed. Engl., EXERCISES
1997, 36, 1669.
315. (a) G.I. Park, S.S. Lim, J.S. Choi, I.K. Song, and W.Y. 1. Compare clays, heteropolyacids, and zeolites as
Lee, J. Catal., 1998, 178, 378. catalysts for organic reactions.
(b) J.K. Lee, I.K. Song, and W.Y. Lee, J. Mol. Catal. A. 2. Pick out the acidic and basic catalysts in the reac-
Chem., 1997, 120, 207.
tions in a volume of Organic Syntheses. Which
316. I.K. Song, J.K. Lee, and W.Y. Lee, Appl. Catal. A, 1994,
one might be replaced with solid acids and bases?
119, 107.
317. D.E. Katsoulis, U.S. patent 5,391,638 1995.
What advantages might there be to doing this?
318. M. Inoue and T. Yamase, Bull. Chem. Soc. Japan, 1995, 3. Devise a system of more meaningful names for ze-
68, 3055. olites.
319. P. Botella, A. Corina and J.M. Lopez-Nieto, J. Cotal., 4. Select a reaction that requires a stoichiometric
1999, 185, 371. amount of aluminum chloride as a catalyst. Try
320. (a) A. Corma, V. Fornes, J. Martinez-Triguero and S.B. running it with a rare earth triflate.
Pergher, J. Catal, 1999, 186, 57. 5. Suggest some reactions that might be more selec-
(b) A. Corma, U. Diaz, M.E. Domine and V. Fornes, tive if run in pillared clays. What separations
Angew. Chem. Int. Ed. Engl., 2000, 39, 1499; Chem. might be run with such clays?
Commun., 2000, 137. 6. How would you characterize a new zeolite or pil-
321. S.E. Sen, S.M. Smith and K.A. Sullivan, Tetrahedron, lared clay or heteropolyacid?
1999, 55, 12657. 7. Having found a zeolite catalyst for a reaction, how
322. B. Coq, D. Tichit and S. Ribet, J. Catal., 2000, 189, 117. would you optimize it?
8. Can you think of a reaction that might be im-
RECOMMENDED READING proved by reactive distillation (i.e., one that has
not already been run in this way)?
1. G. Perot and M. Guisnet. J Mol Catal 1990, 61:173. 9. What is the potential of carbon molecular sieves?
2. K. Tanabe. Appl Catal A 1994, 113:147. 10. If you have never run a catalytic vapor-phase re-
3. M. Misono and T. Okuhara. Chemtech 1993, 23(11):23. action in a hot tube, pick one that could use a solid
4. J.M. Thomas. Angew Chem Int Ed Engl 1994, 33:931–933. acid or base as a catalyst and try it.
5. Y. Izumi, K. Urabe and M Onaka. Zeolite Clay and Het- 11. Predict areas where high-surface–area Nafion
eropoly Acid in Organic Reactions. VCH, Weinheim, might be able to replace the use of hydrogen fluo-
1992:1,2,21,22,99–103. ride and concentrated sulfuric acid as catalysts.
7
Chemical Separations
I. THE GENERAL PICTURE
Separations1 use 6% of the total energy consumed by in-
dustry in the United States.2 They can account for up to
70% of plant costs. The many types include (a) removal of
a catalyst, (b) removal of unchanged starting material, (c)
removal of by-products, (d) recovery of solvent, or other,
from a reaction mixture. Common separations involve (a)
aromatic from aliphatic, (b) substituted from unsubstituted,
(c) linear from branched, (d) positional isomers, (e) di-
astereoisomers and enantiomers, (f) small molecules from
polymers, (g) one polymer from another, (h) charged from
uncharged, (i) one metal ion from another, (j) one anion
from another, and so forth. The traditional methods have
not been entirely satisfactory. Distillation becomes more
difficult with heat-sensitive materials, close-boiling mix-
tures, and azeotropes. Crystallization may not be as selec-
tive as desirable and may leave part of the product in the
mother liquor as waste.3 Extraction may not be completely
selective and may involve the use of large volumes of sol-
vents, frequently with pH changes that result in waste salts.
Chromatography4 is fine for small amounts and analytical
purposes, but it becomes cumbersome on an industrial
scale. However, simulated moving bed chromatography (a
method in which much of the solvent is recirculated and the
inlets and outlets are moved as the profile of the material
moves through the column) is making the technique more
practical and economical for fine chemicals production.5
The goals of improved separations6 include (a) saving
energy, (b) reducing waste, (c) avoiding the generation of
waste salts, (d) minimizing recycle, (e) avoiding or mini-
mizing the use of organic solvents, and (f) saving money.
Current practice for preventing further reaction of the de-
sired product may involve energy-intensive quenching and
running to partial conversion with much recycle. An exam-
175
ple is the oxidation of methanol to formaldehyde with oxy-
gen over a silver catalyst at 700°C, followed by quick
quenching to 150°C to prevent further oxidation to formic
acid.7 A common method of removing an acid catalyst
from a reaction mixture is to wash the mixture (in a solvent)
with a mild base in water, which produces waste salts. The
use of supported reagents and solid catalysts, which can be
recovered for reuse by centrifugation or filtration to avoid
this, was covered in Chap. 5 and 6. To these must be added
a third method, standing acoustical waves of ultrasound,
which has been used in the separation of cells and blood
samples.8
The use of catalysts based on polymers with inverse
temperature solubility, often copolymers of N-isopropy-
lacrylamide, to allow recovery by raising the temperature
to precipitate the polymer for filtration,9 was mentioned in
Chap. 5. The opposite, if the catalyst is soluble hot, but not
cold, has also been used in ruthenium-catalyzed additions
to the triple bonds of acetylenes (7.1).10 The long aliphatic
tail of the phosphine ligand caused the catalyst to be insol-
uble at room temperature so that it could be recovered by
filtration. There was no loss in yield or selectivity after
seven cycles of use. A phosphine-modified poly(N-iso-
propylacrylamide) in 90% aqueous ethanol/heptane has
been used in the hydrogenation of 1-olefins.11 The mixture
is biphasic at 22°C, but one phase at 70°C, at which the re-
action takes place. This is still not ideal, because it takes en-
ergy to heat and cool, and it still uses flammable solvents.
Physical methods of separation are preferred to those
using chemical reagents or organic solvents. These are the
standard methods of separation of minerals. Iron oxides
can be recovered magnetically.12 The iron oxide in kaolin
clay is removed by high-intensity magnetic separation. The
treated clay is used as a filler for paper. Ores can be sepa-
rated by a variety of methods involving radiation. If the
176
where the Catalyst is [Ru(–OCOH)(CO)2((C6H5)2P(CH2CH2)50CH2CH3)]
7.1
pieces of ore are passed by a sensor one at a time, the de-
sired type can be selected by infrared, ultraviolet, visible,
or X-ray radiation. A jet of air is used to remove the se-
lected pieces. This method is also applicable to the sorting
of cans, bottles, and packages in mixed solid waste. It does
have trouble when a container is made of more than one
material, such as a steel can with an aluminum lid. Thus,
there is an incentive to make containers, their caps, lids,
and labels, all of the same material. This method is much
easier than processes that dissolve the mixed plastics in a
solvent and then try to separate them by differential pre-
cipitation. Machine vision that picks out a particular image
pattern has been used to remove aflatoxin-contaminated
nuts from a stream of pistachios passing at the rate of 163-
k/channel per hour with 97.8% selectivity.13 The chemical
industry is making increasing use of these and other sens-
ing techniques for on-line monitoring of reaction mixtures
in plants. They offer the advantage of instantaneous infor-
mation, without having to wait for the laboratory to per-
form analyses. They also avoid the waste and disposal
problems associated with the unused portions of materials
taken for analysis in the laboratory. They should lead to
higher yields.
Separation by density is often used in sink–float tech-
niques. In minerals processing, the bath is often a slurry of
magnetite (Fe3O4). The magnetite is easy to remove mag-
netically. Flotation is a common method of concentrating
ores14 and removing ink from paper during recycling. In
the flotation of minerals, particles are made hydrophobic
with a collector, and a frothing agent is added. Air is bub-
bled through the system and the ore-laden froth is col-
lected. A depressant is used sometimes to make unwanted
accompanying minerals hydrophilic so that they will sink.
Hydrometallurgy, in which the minerals are dissolved, is
used occasionally.15 The metal ion is removed with a spe-
cial hydrophobic chelating agent in a hydrocarbon such as
kerosene. It is then taken into water again by treatment with
acid for collection by electrolytic deposition. Physical sep-
arations on the usual chemical mixtures involve the use of
micro- and mesoporous solids, such as the pillared clays
Chapter 7
and zeolites discussed in Chap. 6. Other such methods will
be covered later in this chapter.
Magnetic beads are available for some bioseparations,16
which are often more complicated than the usual chemical
separations.17 An antibody can be placed on them for an
antigen that is to be separated. Compared with affinity
chromatography in a column, the beads offer no plugging
with cell debris or channeling. They have been used in
immunoassays for pesticides and polychlorinated
biphenyls.18 Iron oxide-filled ion-exchange resins have
been used to recover zinc ion from wastewater.19 The waste
stream flows through a slurry of the resin particles. After
removal of the zinc by acid, the resin can be reused. Mag-
netite-impregnated styrene–divinylbenzene copolymer
resins have also been used for combinatorial synthesis of
polypeptides.20 This simplified the splitting and mixing
procedure. Resin beads containing a metal ion held by a
tetradentate chelating agent are marketed for the separation
of histidine-containing proteins.21 The metal may not be
iron. A process that uses magnetic particles (30 nm–25
m) coated with selective extractants is said to be cheaper
and faster than ion-exchange resins for the recovery of cad-
mium, zinc, transuranic elements, and such, from dilute
waste streams.22
The best approach to improving separations is to work
toward reactions that achieve 100% yields at 100% con-
versions. Frequently, this will require more selective cata-
lysts. The previous chapter contained an example moving
in this direction. Toluene was disproportionated to benzene
and xylenes using a silica-modified zeolite catalyst.23 After
removal of benzene and unchanged toluene by distillation,
the xylene remaining was a 99% para-isomer. It was clean
enough to put directly into the process of oxidation to
terephthalic acid. This avoided the usual separation of
xylenes by crystallization or by a molecular sieve. There
are times when an equilibrium can be shifted by removal of
a product or by-product continuously to give 100% con-
version. The familiar esterification with azeotropic re-
moval of water or removal of water with a molecular sieve
is an example.
Chemical Separations
Reactive distillation24 is a method of removing the prod-
uct from the reaction zone as it is formed, so that further re-
action does not occur. An example cited in the preceding
chapter involved running ethylene into a column of molec-
ular sieve catalyst containing refluxing benzene. The prod-
uct ethylbenzene (needed for the production of styrene)
collected in the distillation pot with minimal dialkylation.25
Any diethylbenzene that did form was transalkylated with
benzene to give more ethylbenzene, using the same cata-
lyst. The result was that ethylbenzene was obtained with
99.7% specificity at 100% conversion. A second example
is the preparation of tert-butyl methyl ether for use as an
additive to gasoline, during which up to 99.99% conversion
of the isobutylene is achieved.26 The ether flows downward
from the column of catalyst into the distillation pot, while
the isobutylene–methanol azeotrope is removed continu-
ously and recycled to the reaction section. Continuous ex-
traction with methylisobutylketone has been used to
achieve over 90% conversion of fructose to 5-hydrox-
ymethylfurfural using an H-mordenite catalyst.27
It is also possible to separate some mixtures by reacting
out a desired compound under conditions in which the oth-
ers present will not react. The C5 refinery stream can be
heated gently until the cyclopentadiene present has dimer-
ized to dicyclopentadiene. The other C5 compounds can
then be distilled off.28 It is also possible to separate
isobutene from mixed butenes by acid-catalyzed hydration
to tert-butyl alcohol or addition of methanol to produce
tert-butyl methyl ether.29 The success of these methods
hinges on the products being useful, as such, or being re-
convertible to the original compounds. Dicyclopentadiene
can be cracked to cyclopentadiene. The tert-butyl alcohol
can be dehydrated to isobutylene. No matter what the sep-
aration technique is, chemical reaction or adsorption, it is
important to be able to recover the material easily in an en-
ergy-efficient way. With adsorption, the usual methods are
heating or evacuation or a combination of the two.
Another useful separation technique for gas–liquid–liq-
uid systems30 involves catalysts that are only soluble in one
of two phases. An outstanding example was cited in Chap.
1. The hydroformylation of propylene to produce bu-
tyraldehydes (in the Ruhrchemie/Rhone–Poulenc process)
is done by passing propylene gas into an aqueous solution
7.2
177
of a ruthenium catalyst.31 The product can be removed con-
tinuously as a separate layer. Union Carbide has devised a
variant of this process with added N-methylpyrrolidone
that extends it to higher olefins, such as octene, dodecene,
styrene, and dienes.32 Another group added ethanol to the
water so that 1-octene could be hydroformylated.33 A fur-
ther variation is seen in the carboxylation of styrene in 98%
yield with carbon monoxide in toluene/water using a water-
soluble palladium catalyst.34 Another example is the Shell
process for higher olefins in which ethylene is passed into
a diol containing an organonickel catalyst.35 The
oligomeric -olefins form a second phase that is easy to
separate. The best examples are those that require no or-
ganic solvent.
Nonvolatile ionic liquids have considerable potential as
media for reactions,36 such as that shown (7.2).37 The prod-
uct was separated by decantation. The ionic liquid layer
could be reused several times, with no loss in catalytic ac-
tivity. The tetrafluoroborate and hexafluorophosphate salts
are stable to air and to water. The tetrachloroaluminate,
which can be used as both catalyst and medium in acylation
and alkylation reactions, is sensitive to moisture. A wide
variety of inorganic and organic materials, including some
polymers, are soluble in ionic liquids. Ionic liquids can be
used in liquid–liquid extractions instead of volatile organic
solvents.38 The product is recovered from the ionic liquid
by evaporation. Examples of the use of such ionic liquids
include the dimerization of propylene, using an ethylalu-
minum chloride salt and a nickel phosphine, during which
the product separates as a separate layer,39 the metathesis
of 2-pentene to 2-butene and 3-hexene with a tungsten cat-
alyst,40 and catalytic hydrogenation of the double bonds,
but not the nitrile groups, in poly(acrylonitrile-co-1,3-buta-
diene) using a ruthenium catalyst in toluene.41 In the last
example, the ionic liquid containing the catalyst could be
separated by decantation and reused several times without
any significant loss of activity or selectivity. If the organic
product remains dissolved in the ionic liquid and is rela-
tively nonvolatile, it can be recovered by extraction with
supercritical carbon dioxide.42 (Other uses of supercritical
fluids are given in Chap. 8.)
Phase-separable homogeneous catalysis43 also includes
fluorous biphasic systems.44 The latter use a liquid fluoro-
178
carbon that is insoluble in organic solvents at 25°C. On
heating to 60°C, or more, the mixture becomes homoge-
neous, and the reaction takes place. On cooling to 25°C, the
product separates. The fluorocarbon phase, which contains
the catalyst, can be reused. For the system to work, perflu-
oroalkyl groups have to be inserted into the ligands for
the metal catalysts and, sometimes, into the reagents. A
typical example is the hydroformylation of 1-decene with
hydrogen and carbon monoxide in 50:50 toluene/
perfluoro(methylcyclohexane) at 100°C using a HRh
(CO){P[CH2CH2(CF2)5CF3]3}3 catalyst.45 At 98% conver-
sion, the selectivity to aldehydes was 90%, and the selec-
tivity to 2-olefins, which did not react further, was 10%. In
nine reaction–separation cycles, the total turnover was
more than 35,000, with a loss of 1.18 ppm Rh per mole of
undecanals. Although such systems may be useful in spe-
cialized cases, they will probably remain too expensive for
general industrial use.
Systems with two aqueous phases have been used in the
separation of proteins and metal ions.46 These involve wa-
ter-soluble polymers, such as poly(ethylene glycol), with
or without salts, such as potassium phosphate.47 Such sys-
tems eliminate the need for volatile organic solvents. A
typical example is the separation of myoglobin with aque-
ous poly(N-vinylacetamide)–dextran, the protein going to
the bottom phase containing the dextran.48
In theory, at least, there may be exceptions to the gener-
alization that pH changes to cause separation produce
waste salts. The sodium hydroxide used to extract a phenol
into water (Eq. 7.1) could be recycled.
ArOH  NaOH → ArONa
CO
→
2
ArOH  Na2CO3
 branes for continuous use or in columns for cyclical use.
↓heat (Eq. 7.1)
Na20  CO2
 recognition.
↓H20
NaOH
The reaction would have to be run such that a minimum of
water would need to be removed by reverse osmosis or by
evaporation. Carbon dioxide under pressure has been used
to free 6-hydroxy-2-naphthoic acid from its potassium salt,
to recover the acid and recycle potassium carbonate.49 Am-
monia or tertiary amines can be used to separate carboxylic
acids. The ammonia or amine can be recovered by heating
under a vacuum. This type of reaction is used in some floor
polishes. The polymer containing the carboxylic acid
groups is soluble in aqueous ammonia until applied. It loses
its solubility in water when the ammonia evaporates. How-
ever, the polish can be stripped from the floor by the use of
Chapter 7
fresh aqueous ammonia. Trimethylamine, in ketones such
as methyl ethyl ketone or methyl isobutyl ketone, has been
used to recover lactic and succinic acids from their aqueous
solutions. The free acids were obtained and the base recov-
ered for recycle by heating the salts.50
There are also examples for which there is no need to
separate a catalyst, because it can be left in the product
without adverse effects. Magnesium chloride-supported
catalysts for the polymerization of propylene attain such
high mileage that they can be left in the polymer. Earlier
less-efficient catalysts had to be removed by an acidic ex-
traction process that produced titanium- and aluminum-
containing wastes. The earlier processes also produced
heptane-soluble polymer that had to be removed, and,
sometimes, ended up as waste. The newer processes pro-
duce so little that it can be left in the product. Thus, im-
proved catalysts have eliminated waste.
II. INCLUSION COMPOUNDS
The use of zeolites, molecular sieves, and pillared clays to
sort molecules by size and shape was described in Chap.
6. Some organic molecules also contain cavities or chan-
nels that guests can fit into and thus separate them from
other compounds. The host–guest combinations are often
referred to as inclusion compounds or clathrates.51 The
cyclodextrins—conical molecules containing six, seven,
or eight glucose units in rings—perhaps, are the most
common. They were covered in Chap. 5. Others include
crown ethers, cryptates, cyclophanes, and calixarenes, all
of which are more expensive than cyclodextrins.52 The
price may not matter if they can be recovered and used re-
peatedly. The best systems might insert them in mem-
The goal is to approach the exquisite selectivity of bio-
logical systems. This is part of current work in molecular
The guest must have a suitable size and shape to fit into
the host. Cavities lined with nonpolar groups may favor
nonpolar guests, whereas a polar lining may favor a polar
guest. Host channels may favor linear molecules. Host
cages may favor spherical molecules. Hydrogen bonding of
amides with OH and NH may stabilize some structures.
The cavities are usually 4–8 Å in diameter. Inclusion com-
pounds can be formed by putting the host into excess guest,
or putting the two into a common solvent. Sometimes, the
complex will form on exposure of the crystalline host to the
vapor of a guest. Sometimes, the two can just be ground to-
gether. The stability of the inclusion compounds varies
greatly. If the compound depends on the crystal structure of
the host, the guest will be liberated if the inclusion com-
Chemical Separations 179

7.3

pound is dissolved. This may be a simple way to recover Occasionally, a chiral diol can serve as host for one op-
the guest after a separation. Some inclusion compounds are tical isomer (e.g., an epoxide), allowing the other one to be
stable only in the presence of excess guest. Others may be distilled out. The guest optical isomer can then be recov-
so stable that they must be heated strongly or placed in a ered by stronger heating. A quaternary ammonium salt, de-
substantial vacuum to recover the guest. rived from the amino acid leucine, has been used to resolve
Urea is an inexpensive material that crystallizes with 1,1- bi-2-naphthol (7.4) by formation of an inclusion
roughly 5-Å–diameter channels in a structure held to- compound.57
gether by hydrogen bonding. Linear alkanes, usually with Hydrazine can be stabilized by formation of an inclu-
six or more carbon atoms, can fit into these channels.53 As sion compound with hydroquinone.58 Uncomplexed anhy-
long as the linear alkyl group is present, other groups, drous hydrazine can be explosive. Highly toxic dimethyl
such as aldehyde, ketone, ether, ester, carboxylic acid, sulfate can be handled more easily as an inclusion com-
hydroxyl, amine, nitrile, mercaptan, sulfide, and aromatic pound with toxic 18-crown-6. Both of these toxic com-
ring can also be present in the guest. If urea is crystallized pounds could be avoided through the use of dimethyl car-
from a methanolic solution containing fatty acids, the bonate (as described in Chap. 2). Reactive intermediates,
such as benzyne, have been stabilized by generating them
crystals are enriched in the saturated acids over the unsat-
inside hosts.59 Even the noble gas xenon can be trapped re-
urated ones. Monounsaturated acids fit better than polyun-
versibly by hosts such as a cryptophane, 4-tert-butyl-
saturated ones. The crystals can be filtered off and dis-
calix[4]arene or -cyclodextrin.60
solved in water to liberate the fatty acids. By using such
A variety of substituted ureas have been used to form in-
techniques to eliminate saturated and polyunsaturated clusion compounds.61 Curcurbituril, made from urea, gly-
fatty acids, 97–99% oleic acid has been obtained from oxal, and formaldehyde is a band-shaped molecule with a
olive oil’s fatty acids.54 It is possible that this method 4-Å hole at the top and the bottom connected to a 5.5-Å
could be applied to biodiesel fuel obtained by the
methanolysis or ethanolysis of rapeseed oil, to eliminate
the saturated esters that tend to crystallize out in cold win-
ter weather. An untried alternative might be to use a de-
saturase enzyme to convert the saturated ester in the orig-
inal mixture to an unsaturated one.
Inserting the guest into the host can sometimes improve
the selectivity of its reactions. The polymerization of 1,3-
butadiene in urea crystals preferentially leads to the crys-
talline 1,4-trans polymer.55 Such solid-state reactions can
improve the selectivity in many reactions.56 If performed
with a chiral diol, the reaction can give products with high
enantioselectivity (7.3). 7.4
180
NH2CONH2 + OHCCHO + HCHO
7.5
cavity (7.5). It forms strong complexes with some diamines
(e.g., 1,6-diaminohexane) and with alkylammonium ions,
such as protonated 1-aminopentane.62
A basket-shaped host that is a crown ether containing a bi-
cyclic urea structure (7.6) (where R is phenyl) has been used
to bind the herbicide Paraquat analogue (7.7) (where the an-
ion is hexafluorophosphate) and some polymeric derivatives
of it with K up to 57,000.63 Even stronger binding with a K of
7 million has been obtained with a cyclic urea porphyrin.64
Rebek and co-workers have studied the self-assembly of
molecules containing substituted ureas.65 Dimerization of
two calixarenes (where Bn is benzyl and Ar is 4-fluo-
rophenyl;) (7.8) by hydrogen bonding produces a host that
encapsulates benzene, fluorobenzene, p-difluorobenzene,
and pyrazine, but not toluene.
The strongest complex was that of difluorobenzene. Sta-
bility favors the best fit that leaves no empty space in the
cavity. The self-assembled dimer of the urea in (7.9) (where
R  ethoxycarbonyl) encapsulated methane but not ethane:
Hydrogen bonding is also important in the sheet-like
7.6
7.7
Chapter 7
guanidinium sulfonate hosts, for which the gallery height
can be varied from 3.0 to 11.5 Å by changing the sul-
fonate.66 For example, the distance is 3 Å for dithionate,
5.5 Å for ethane-1,2-disulfonate, 9.5 Å for 2,6-naphthalene
disulfonate, and 11 Å for 4,4-biphenyldisulfonate. A typi-
cal preparation involves crystallization from a 2:1 mixture
of guanidinium hydrochloride and 4,4-biphenyldisulfonic
acid in methanol in the presence of a guest. Typical guests
include acetonitrile, benzonitrile, m-xylene, styrene, and
toluene.
Several diols form inclusion compounds.67 The bicyclic
one shown (7.10) contains tubular canals that guests can fit
into.68 The crystals form inclusion compounds with the va-
por of 1,2-dimethoxyethane, 1,2-dichloroethane, 1,4-diox-
ane, ethyl acetate, toluene, chlorobenzene, and others. The
tetrols (7.11 and 7.12) also form inclusion compounds with
various guests.
Compound 7.11 favors acetone over isopropyl alcohol,
acetonitrile over isopropyl alcohol, acetonitrile over
methanol, and pyridine over methanol.69 Compound 7.12 is
7.8
Chemical Separations
7.9
described as an organic analogue of zeolites with hydro-
gen-bonded molecular sheets.70 Esters, such as ethyl ben-
zoate, and ketones, such as 5-nonanone, can be guests.
The octasulfide (where Ar is 3,4-dimethylphenyl;)
(7.13) can act as a host for 1,4-dioxane, N,N-dimethylfor-
mamide, tetrahydrofuran, toluene, tert-butyl alcohol, ethyl
acetate, limonene, and o-xylene.71
Some pyrazolones can also form inclusion compounds.
Compound (7.14) (in which Ar is meta- or para-pheny-
lene) forms inclusion compounds with methanol, ethanol,
isopropyl alcohol, acetone, 2-butanone, tetrahydrofuran,
and 1,4-dioxane, often with two guest molecules for one
host molecule.72
Carboxylic acids can also form clathrates. Xylene iso-
mers can be separated by formation of clathrates with 1,1-
binaphthyl-2,2-dicarboxylic acid.73 m-Xylene does not
form a complex. The o-xylene complex decomposes at
7.10
7.11
181
7.12
50–100°C, and the p-xylene complex at 100–120°C. Charge
transfer is a factor in the host–guest complex of 4-methyl-
3,5-dinitrobenzoic acid with 2,6-dimethylnaphthalene.74
Charge transfer with tetranitrofluorenone has also been used
to remove 60% of the dialkyldibenzothiophenes from
petroleum that contains 1920 ppm sulfur, although no in-
clusion compound is involved.75 As polynitro compounds
are often explosive, a better charge acceptor is needed.
The host (7.15) was found by combinatorial synthesis
(from a library of 100 salts): It forms host–guest complexes
with several alcohols, ketones, xylenes, and others (e.g.,
2:3 with methanol, 1:1 with ethanol, 2:2 with acetone, and
2:1 with acetonitrile).76
7.13
7.14
182
7.15
Cobalt, nickel, and zinc salts of 1,3,5-benzenetricar-
boxylic acid are solids with 4- to 5-Å pores, which can of-
ten accommodate ammonia, ethanol, or water, but not
larger molecules, as guests.77 Cobalt and zinc terephtha-
lates can also act as hosts for molecules such as pyrazine.78
The purpose in showing these rather exotic structures
is to indicate the many possibilities for selectivity for
shapes,79 some of which are not possible with zeolites,
pillared clays, on others. Sometimes, the host structure
adjusts to the guest to give an induced fit. By using this
method, it is possible to select compounds based solely on
size. For practical use, it may often be necessary to im-
mobilize these structures on supports or place them in
membranes.
7.16
Chapter 7
High selectivity can be obtained by imprinting polymers
with neutral molecules.80 In this process, a cross-linked
polymer is prepared in the presence of a template. Then the
template is removed by solvent extraction. The extracted
polymer is then used to pick up the template molecules
from other sources. Among the examples in the literature
are some that deal with atrazine (an herbicide), cholesterol,
other sterols, dipeptides, N-acetyltryptophane resolution
(L-isomer favored by a factor of 6), adenine, and barbitu-
rates.81 The polymerizations in the first two examples, are
shown in (7.16) (The cross-linking comonomer with the
cholesterol-containing monomer was ethylenebis-
methacrylate. The cholesterol was cleaved from the poly-
mer with sodium hydroxide in methanol.)
III. SEPARATION OF IONS
The desire to attain near-biological specificity in the sepa-
ration of ions was mentioned in Chap. 4. Some progress is
being made in this direction with ligands that form fairly
specific complexes. These may not be inclusion com-
pounds, but at least some involve encapsulation of the ion.
These have been developed by “tuning” macrocycles by
varying ring size, ring substitution, and the donor set of
oxygen, nitrogen, and sulfur atoms.82 For calix[n]arenes, it
can involve varying the ring size, as well as the extent and
type of substitution on both the aromatic rings and the hy-
Chemical Separations 183

droxyl groups.83 Devising more specific receptors for an-

ions may also involve guanidinium salts and other azonia
compounds, as well as inclusion of a transition metal ion in
the macrocycle.84
Casnati and co-workers have devised a calixarene
crown ether (7.17) that shows a preference for potassium
over sodium of 22,000.85 A macrocyclic polyether with at-
tached 8-hydroxyquinoline groups (7.18) favors barium
over other alkaline earth cations by a factor of more than 10
million.86 Compound (7.19) shows a preference of magne-
sium over calcium of 590.87 Compound (7.20) has the
highest known binding constant for Ag(I), log K  19.6.88
There is also an active search for selective anion accep- 7.19
tors.89 The cryptate (7.21) favors fluoride over chloride by
a factor of 40 million.90
Many bodies of water become eutrophic when excess
phosphate from detergents and fertilizer washes in. This
overenrichment results in undesirable algal blooms. Agents
that complex phosphate may allow it to be removed from
treated wastewater, recovered, and reused. The first com-
plexing agent (7.22) (where X  S) complexes dihydrogen
phosphate with a K of 820 and acetate with a K of 470;
chloride, hydrogen sulfate, nitrate, and perchlorate are held
much more weakly.91 The K for the second one with phos-
phate (7.23; where R is H) is 12,000.92 7.20
Strong complexes of phosphates are known for 7.22
compound (7.24) (K  1.9  105 for H2PO 4 93
) and the
zinc(II) complex of the (7.25) (log K  5.8–7.9 for The pyridinium salt (7.26) is a receptor for tricarboxylic
ROPO4).94 acids with log K  4.5–5.0.95 The trisguanidinium salt
(7.27) has a binding constant for citrate of 6.9  103.96
Sugars such as fructose and glucose, can be complexed
with the arylboronic acid (7.28), presumably through the
formation of cyclic boronates.97 (Although not ions, the
sugars are included here because of the similarity of the
complexing agent to those effective for ions.) A bisboronic
acid of a -oxobis [porphinatoiron(III)] forms complexes
with glucose and galactose, with association constants of

7.17

7.18 7.21
184 Chapter 7

7.22

7.23 7.24

7.25 7.26
Chemical Separations
7.27
7.28
104–105.98 Fructose can be separated from glucose by using
a liquid membrane with a similar boronic acid in microp-
orous polypropylene.99 When glucose isomerase is in-
cluded in the liquid, the output can be more than 80% fruc-
tose. High-fructose corn syrup is used widely as a
sweetener.
IV. MEMBRANE SEPARATIONS
Membranes can be used to separate molecules that differ in
size, polarity, ionic character, hydrophilicity, and hy-
drophobicity.100 Their use is less energy-intensive than dis-
tillation. They can often separate azeotropes and close-boil-
ing mixtures. They can sometimes replace traditional
methods, such as solvent extraction, precipitation, and
chromatography, that can be inefficient, expensive, or may
result in the loss of substantial amounts of product. Ther-
mally and chemically sensitive molecules can be handled.
Membranes can be porous or nonporous, solid or liquid, or-
ganic or inorganic.
Microfiltration101 membranes have 0.1- to 10-m pores.
They can be used to remove bacteria and viruses from
drinking water, as an alternative to chlorination.102 The re-
moval of viruses is most effective when the membrane is
made of poly(N-benzyl-4-vinylpyridinium chloride).103 Ul-
185
trafiltration membranes have 0.002- to 0.05-m pores.
They can remove macromolecules such as proteins. An ex-
ample is the concentration of cheese whey, the liquid left
when cheese is made. Ultrafiltration has also been used for
the recovery of water-soluble paints in the rinse water from
coating automobiles, oil from aqueous emulsions of metal-
working fluids, polyvinyl alcohol from textile desizing,
and in the removal of polymeric materials from drugs, such
alkaloids. In the refining of vegetable oils, it removes
100% of the phospholipids, 80–85% of the free fatty acids,
and most of the pigments.104 This process eliminates wa-
ter–acid treatment to remove the phospholipids, base to re-
move the free fatty acids, and deodorization by vacuum
stripping. It can also be used for small organic molecules
(e.g., 2-phenylethanol) held in micelles (in water) that are
too large to pass through the pore.105
Reverse osmosis106 uses membranes with 5- to 20-A
pores or no pores at all. Some authors add a category called
nanofiltration that is roughly between ultrafiltration and re-
verse osmosis. A membrane with 20-Å pores retained
90–98% of sugars and magnesium sulfate, but passed
sodium chloride.107 Acidic copper sulfate-containing
wastewater was concentrated by reverse osmosis, then
passed through a nanofiltration membrane to recover the
copper sulfate. The recovered water was recycled to the
process. This is an appropriate option for electroplating
waste. At low pH, acetic acid and lactic acid are largely
undissociated and pass through such a membrane. At
higher pH, they do not go through. These acids can also be
separated by Nafion membranes,108 weak base ion-ex-
change resins,109 and by extraction with long-chain tertiary
amines.110 Cheese whey, which contains 4–6% sodium
chloride, and soy sauce, which contains 18% salt, can be
desalted in this way. Such a process can replace more ex-
pensive salting-out procedures, in which salts are added to
cause a product to separate.111 The fatty acids, oils, and fats
left in the wastewater from oil-processing plants can be re-
covered in this way.112 An aromatic polyamide membrane
for desalination by reverse osmosis had improved flux,
with no loss in ion rejection after treatment with hydroflu-
oric acid.113
Electrodialysis uses stacks of pairs of anion- and cation-
exchange membranes in deionizing water and in recovery of
formic, acetic, lactic, gluconic, citric, succinic, and glu-
tamic acids from their sodium and potassium salts in
fermentation broths.114 This may have an advantage over
processes that involve purification through calcium salts.
Electrodialytic bipolar membranes have been used to re-
cover concentrated mineral acids from dilute solution.115
They can be used to convert sodium chloride to hydrogen
chloride and sodium hydroxide in a process that avoids the
use of chlorine.116 Soy protein has been precipitated by
186
electroacidification with bipolar membranes.117 No chemi-
cal acids or bases were needed. The effluents could be
reused. The product was just as acceptable as a conventional
one. Membranes of perfluorinated sulfonic acid polymers,
such as Nafion, pass water and cations freely, but are im-
permeable to anions.118 They are used in electrochemical
processes, such as the electrolysis of aqueous sodium chlo-
ride to produce chlorine and sodium hydroxide. They are re-
placing polluting mercury cells in this application.
Membranes can be made in various shapes. The plate
and frame types have less surface area per unit of space
than the spirally wound ones; hollow fiber ones119 have the
most. In commercial reverse osmosis, spirally wound ones
are used in 75% of the cases and hollow fibers in 25%.
Fouling can be a problem with membranes. A prefilter120 is
used to remove larger particles. The liquid can be flowed
across a surface instead of directly at it to reduce fouling.
High-frequency flow reversal and local shear enhancement
(possibly by ultrasound) can reduce fouling.121 Mechanical
vibration at 60 Hz is said to increase the flow rate five-
fold.122 If the particles causing the fouling have a net sur-
face charge, they can be repelled by a membrane with the
same surface charge.123 The use of an electromagnetic field
with a conventional reverse osmosis membrane reduced
fouling severalfold and doubled the flux. 124 Sulfonated
polysulfone membranes are fouled less by proteins.125 The
fouling of membranes by natural organic matter is delaying
the acceptance of the technology for purifying drinking wa-
ter.126 The problem is being studied intensively. A clever
system has been used to prepare a self-cleaning membrane
for the concentration of a solution of casein. Trypsin is at-
tached to the aminated polysulfone membrane with glu-
taraldehyde.127 Any proteins that settle on the membrane
are digested. When the fouling impurities in drinking water
are better identified, such an enzymatic technique may be
applicable. If an inorganic membrane becomes fouled with
organic matter, the latter can be burned off. If the mem-
brane fouled very often, this could be inconvenient for a
water treatment plant.
Microporous membranes that are not wetted by the liq-
uid on either side can be used to concentrate solutes to high
levels at low temperature and pressure. The volatile com-
ponent crosses the vapor gap to the receiving liquid. This
technique of osmotic distillation has been used to concen-
trate fruit and vegetable juices, as well as pharmaceuticals,
sugars, proteins, and salts of carboxylic acids.128
The pores of microporous membranes can be filled with
liquids to form liquid membranes that can be used in sepa-
rations.129 Transport through such membranes is often fa-
cilitated by the addition of a carrier to the liquid to improve
the separation factor or the flux rate. A solution of a long-
chain tertiary aliphatic amine in kerosene in the pores of a
Chapter 7
poly(tetrafluoroethylene) membrane was used to separate
nickel(II) ion from cobalt(II) and copper(II) ions.130 The
cobalt and copper ions passed through, but the nickel ion
did not. (The separation of nickel from cobalt in ores is a
long-standing problem.) Visser and co-workers have stud-
ied the carrier-mediated transport of ions through liquid
membranes in polymer pores using salicylimine–uranyl
complexes.131 Dihydrogenphosphate ion moved through
140 times as fast as chloride ion. Catecholamines have
been extracted using a boronic acid calixarene in 2-nitro-
phenyl octyl ether (7.29).132 (The analogue with an octade-
cyloxy group meta to the boronic acid group was about
nine times as effective as the one shown.)
This is analogous to the extraction of sugars with
boronic acids described earlier. The recovery of phenylala-
nine from a fermentation broth has been simplified by us-
ing a microporous poly(tetrafluoroethylene) membrane
with tri-n-octylmethylammonium chloride in toluene in the
pores.133 Phenylalanine can also be separated using the
quaternary ammonium salt with 2-nitrophenyl octyl ether
in a cellulose triacetate membrane.134 Kerosene flowing in
hollow fiber membranes can remove 99.9% of organic pol-
lutants, such as benzene, p-dichlorobenzene, chloroform,
and carbon tetrachloride, from wastewater outside the
fibers.135
Anions can be separated by varying the applied poten-
tial across a porous polypropylene membrane with
polypyrrole in the holes.136 Chloride ion had high perme-
ability, whereas sulfate and benzoate had low permeability.
Almost all gas separations are performed with non-
porous membranes.137 The rate of movement through the
membrane depends on the diffusivity and solubility of the
gas in the polymer.138 Diffusion is higher for small
molecules. It is faster in a rubbery polymer than in a glassy
polymer. The selection of nitrogen over pentane in natural
rubber is 10, but in polyvinyl chloride, it is 100,000. The
rate of movement of the gas through the polymer is in-
versely related to the thickness. For a rapid rate, the poly-
mer film should be as thin as possible. For a mechanically
strong defect-free film, the limit is about 20 m. In prac-
tice, a very thin film is placed on a thicker porous structure
of the same or a different material. To obtain a satisfactory
flux rate, the surface area is made as large as possible, of-
ten by the use of hollow fibers. The flux rate can vary with
the temperature and pressure. The driving force for move-
ment through the membrane is a pressure, concentration, or
pH gradient. The separation factor, , usually becomes
lower as the flux rate increases. If the separation factor is
low, it may be necessary to use more than one stage. For
practical use, the membrane must be mechanically, ther-
mally, and chemically stable over a long period and have a
high selectivity for the desired separation.
Chemical Separations
7.29
Common industrial applications include the following
separations: (a) nitrogen and oxygen from air, (b) hydrogen
from refinery gases, (c) hydrogen from ammonia plant off-
gas, (d) carbon dioxide from methane (for natural gas and
landfill gas), (e) carbon monoxide from hydrogen (for ad-
justment of the ratio for hydroformylation of olefins), (f)
helium from methane, (g) hydrogen sulfide from methane
(for natural gas), and (h) organic vapors from air.139 Gas
separation membranes offer low-energy consumption, re-
duced environmental impact, suitable cost effectiveness at
low gas volumes, low maintenance costs, and ease of oper-
ation, with space and weight efficiency.140 Because the
units are modular, it is easy to expand a plant. Some exam-
ples will be given to illustrate the diversity of approaches
used. Nitrogen from commercial hollow fiber membrane
systems is available in 95–99.9% purity.141 Membrane-
based nitrogen costs one-third to one-half as much as liquid
nitrogen. The best separation factors for oxygen over nitro-
gen (8–12, and in one case 26) appear to be with aromatic
polyimides and polytriazoles.142 The permeability was low
where the -valve was 26 at 30°C and this dropped to 13
for the same membrane at 100°C. This membrane had a
separation factor of 169 for hydrogen over nitrogen at the
higher temperature. Polyaniline membranes separate oxy-
gen over nitrogen with an -valve of 14.143 The corre-
sponding values of hydrogen over nitrogen, helium over ni-
trogen, and carbon dioxide over methane are 314, 366, and
78, respectively. Polyaniline can be prepared in the pores of
microporous polypropylene by polymerization of aniline
with ammonium persulfate.144 This gives a strong flexible
membrane. The inclusion of cobalt complexes in mem-
branes for facilitated transport of oxygen often raises the -
187
valve of oxygen over nitrogen to 7–15.145 The flux rate can
also go up. The problem with these systems is one of lim-
ited stability, partly owing to the oxidation of the cobalt
complex. Zeolites and carbon molecular sieves are also
used to separate oxygen from nitrogen.146 The latter have
an -valve of 9–16, but are vulnerable to moisture. To
avoid this, hollow fiber membranes of the molecular sieve
have been coated with copolymers of tetrafluoroethy-
lene.147 The coated material gave an -valve of 200 for hy-
drogen over methane. Air Products has used Li3Co(CN)5 2
HCON(CH3)2 to adsorb more oxygen reversibly than a car-
bon molecular sieve.148 It lost 15% of its activity over 545
cycles in 17 days. It also degraded in moist air. For com-
mercial use, the half-life must be greater than half a year.
There is also interest in separating carbon dioxide from
nitrogen in flue gases. Both have important industrial uses.
The separation factor for carbon dioxide over nitrogen with
polycarbonate and polysulfone membranes149 is 35–40;
with polyethylene glycol in cellulose acetate150 is 22; with
polyether imides containing polyethylene oxide units151 is
70; with an amine modified polyimide152 is 814; with a
copolymer of dimethylaminoethyl methacrylate and acry-
lonitrile153 is 60–90; and with 40% 3-methylsulfolane in
poly(trimethylsilylmethyl methacrylate)154 is more than
40. This last combination also separated out the sulfur
dioxide in stack gas with an -valve for sulfur dioxide over
nitrogen of 395 and sulfur dioxide over carbon dioxide of
29.155 The 3-methylsulfolane is added as a plasticizer to in-
crease the flux rate. For a commercial membrane, it would
have to remain in the membrane and not be evaporated over
a long time period. An alternative is to devise an equivalent
comonomer for use with the trimethylsilylmethyl
188
7.30
7.31
methacrylate. Poly(trimethylsilylmethyl methacrylate)
(7.30) and poly(trimethylsilyl-1-propyne) (7.31) are used
because they have higher gas permeabilities than many
other polymers.156 Work in this area is aimed at increasing
the selectivity at high permeability and at improving the
stability of the polymers under extended use.
The aromatic polyimides, cited earlier, separate carbon
dioxide over methane with -valves of 150–160. Aromatic
polyoxadiazoles have -valves of 100–200.157 The perme-
ability of one aromatic polyimide was improved by two to
four orders of magnitude by carbonizing it on porous alu-
mina,158 the final -valve being 100. In this case, the final
actual membrane was probably a porous carbon molecular
sieve. Facilitated transport has also been used to increase
the separation factor. A porous poly(vinylidene difluoride)
membrane with ethanolamine or diethanolamine in the
pores gave a separation factor of carbon dioxide over
methane of 2000.159 Such a method is less energy-intensive
than when an amine is used in the usual solvent method.
Aromatic polyimides, containing trifluoromethyl
groups, have been used to separate hydrogen over carbon
monoxide, with -values of 26–66 and hydrogen over
methane with -valves of 73–380.160 An -valve of 22 was
obtained with a membrane of a copolymer of methyl
methacrylate and tris (trimethylsiloxy) [
-(methacry-
loxy)propyl] silane, in a process estimated to cost only 40%
of the cost of the present cryogenic distillation.161
Air Products has devised a nanoporous carbon mem-
brane on macroporous alumina that passes hydrocarbons,
such as butane, 100 times faster than hydrogen.162 The hy-
Chapter 7
drocarbon molecules adsorb in the holes and diffuse
through, while blocking the passage of the hydrogen. The
process can recover hydrogen from refinery gases for use,
rather than just sending it to the flare. Olefins can be re-
covered from the nitrogen used in olefin polymerization
plants with a membrane more permeable to the olefin.163
Two stages are needed. Volatile organic compounds, at
concentrations higher than 1% in air, can be recovered eco-
nomically using rubbery membranes of silicone or
polyurethane.164 These include chlorofluorocarbons, hy-
drochlorofluorocarbons, tetrachloroethylene, carbon tetra-
chloride, benzene, toluene, p-xylene, and hexane, with sep-
arations factors of 30–210. This offers an alternative to
carbon adsorption and cold traps for recovery of valuable
compounds, at the same time avoiding air pollution.
Ethylene has been separated from ethane by a silver ni-
trate solution passing countercurrent in a hollow fiber poly-
sulfone.165 This separation has also been performed with the
silver nitrate solution between two sheets of a polysilox-
ane.166 A hydrated silver ion-exchanged Nafion film sepa-
rated 1,5-hexadiene from 1-hexene with separation factors
of 50–80.167 Polyethylene, graft-polymerized with acrylic
acid, then converted to its silver salt, favored isobutylene
over isobutane by a factor of 10. Olefins, such as ethylene,
can be separated from paraffins by electroinduced facili-
tated transport using a Nafion membrane containing copper
ions and platinum.168 A carbon molecular sieve made by py-
rolysis of a polyimide, followed by enlargement of the pores
with water at 400°C selected propylene over propane with
an -valve greater than 100 at 35°C.169
Carbon molecular sieves can also be used to recover flu-
orine-containing gases for recycling at semiconductor
plants.170 (These are potent greenhouse gases.)
The polyetherketone (7.32) has a separation factor of
1.5  106 for water vapor over nitrogen and can be used to
dehumidify gases.171
Chiral membrane separations are also possible. The
modified poly(L-glutamate) (7.33) separated racemic tryp-
tophane completely.172
Inorganic membranes173 are much more expensive than
organic ones, but they have certain advantages.174 In pro-
7.32
Chemical Separations
7.33
cessing foods, they offer ease of sterilization by heating
and resistance to chlorine-containing sterilants. Organic
fouling substances can be burned off. Stack gases do not
have to be cooled before the membrane can be used. They
are also resistant to organic solvents. Ceramic membranes
for micro- and ultrafiltration can last 5–10 years.175 Ce-
ramic membranes can also be produced with pore sizes of
5–100 Å.176 The sol–gel method can be used to place thin
layers on a porous inorganic support.177 Thin layers of sil-
ica can be placed on porous Vycor glass by alternating
treatments with tetrachlorosilane and water.178 The result-
ing membrane had a separation factor for hydrogen over ni-
trogen of 500–1000 at 600°C. It might be used on the tail
gas of an ammonia plant. This same separation has been ac-
complished with an -valve of more than 1000 with a sil-
ica membrane made by chemical vapor deposition of
tetraethoxysilane in the pores of an alumina tube at
400–600°C.179 The membrane was stable to steam at
500°C. Similar ultrathin films have been made by plasma
polymerization of hexamethyldisiloxane.180 Volatile sol-
vents can be removed from air using La2O3-modified
-alumina membranes.181 For removal of acetone from ni-
trogen, the separation factor was about 1000. Up to 99% of
a red anionic dye was removed from wastewater with a ti-
tanium dioxide membrane with 0.2-m pores.182 This is a
simpler process than trying to oxidize the dye in the
wastewater and should allow reuse of the recovered dye.
Membranes of carbon with 100-Å pores can be prepared by
the pyrolysis of mixtures of polyacrylonitrile and other
polymers.183 This is similar to the preparation of graphite
fibers.
Defect-free zeolite films are now available for separa-
tions (also see Chap. 6). They are usually made on a porous
inorganic support.184 These have been used to separate
benzene over p-xylene by an -valve of more than 160, n-
butane over isobutane by one of 88,185 water over propanol
one of 71,186 hydrogen over isobutane with one of 151, hy-
drogen over methane with one of 500,187 and hydrogen
189
over argon with one of 5.3. Zeolites have also been embed-
ded in nickel foil188 and in glassy organic polymers.189 The
latter gave a separation factor of carbon dioxide over
methane of 34. Silicalite molecular sieves have been ap-
plied on porous alumina and stainless steel.190 Using these,
the separation factor for hexane over benzene was more
than 200, for n-octane over isooctane 40, and for hexane
over 2,2-dimethylhexane at 200°C 2000. The silicalite on
sintered stainless steel selectively permeated acetic acid
over water from 5 to 40% solutions. Self-supporting films
of montmorillonite clay have also been prepared.191
Pervaporation is a process in which compounds move
selectively across a membrane in response to a vacuum.192
This a less energetic process than the usual distillation. The
most common use is in the dehydration of ethanol which
needs less than 20% of the energy of the azeotropic distil-
lation process.193 (To remove the remaining water from the
95% ethanol–5% water azeotrope, a hydrocarbon, such as
benzene is added and distillation continued until the water
is removed as a new azeotrope. This is the process that is
being displaced.) The separation factors for water over al-
cohol are high, such as 12,000 for a polymeric quaternary
ammonium salt complex of -carrageenan (a polysaccha-
ride potassium sulfonate from seaweed) with a flux rate of
600 g/m2h;194 6300 for a polycarbonate grafted with 4-
vinylpyridine;195 3000–4500 for blends of polyvinyl alco-
hol with sodium alginate,196 3500 for a polyacrylic
acid–polycationic polymer blend with a flux rate of 1.6
kg/m2h;197 and 1000–2000 for a membrane of polyvinyl al-
cohol–poly(styrenesulfonic acid barium salt).198
The opposite process, the selective removal of ethanol,
is not as easy. It requires a more hydrophobic membrane
and the separation factors are much lower. It has the poten-
tial of being very useful. The yeasts that form ethanol
during fermentation are inhibited by it. This limits the con-
centration of ethanol to 6–20%, depending on the particu-
lar yeast used. If ethanol were removed continuously dur-
ing fermentation, more alcohol could be produced from a
given batch of yeast. Even if the ethanol permeate con-
tained a significant amount of water, this water could be
removed by one of the aforementioned membranes. This
two-membrane process could reduce the price of fuel
ethanol to make it more competitive with gasoline. This
could be part of a switch to a sustainable future that could
help moderate the rate of global warming. Separation fac-
tors for 2.5–10% ethanol in water include 60 for silicalite
in stainless steel,199 about 30 for an aluminum-free ana-
logue of zeolite ZSM-5 in silicone rubber,200 17 for
poly(trimethylsilyl-1-propyne),201 and 12–15 (with a flux
rate of 200g/m2h with no decline in flux over time) for 1%
of poly(dimethylsiloxane) in poly(trimethylsilyl-1-
propyne).202 Poly(trimethylsilyl-1-propyne) oxidizes read-
190
ily in air, so that membranes made of it tend to deteriorate
with age.203 The poly(dimethylsiloxane) may inhibit this
reaction. It is possible that the addition of a polymeric an-
tioxidant would delay aging of the membranes.
Water can be removed from methanol by a membrane
of polyvinyl alcohol cross-linked with polyacrylic acid,
with a separation factor of 465.204 A polymeric hydrazone
of 2,6-pyridinedialdehyde has been used to dehydrate
azeotropes of water with n- and i-propyl alcohol, s- and
tert-butyl alcohol, and tetrahydrofuran.205 The Clostrid-
ium acetobutylicum which is used to produce 1-butanol, is
inhibited by it. Pervaporation through a poly(dimethyl-
siloxane) membrane filled with cyclodextrins, zeolites, or
oleyl alcohol kept the concentration in the broth lower
than 1% and removed the inhibition.206 Acetic acid can be
dehydrated with separation factors of 807 for poly(4-
methyl-1-pentene) grafted with 4-vinylpyridine,207 150
for polyvinyl alcohol cross-linked with glutaraldehyde,208
more than 1300 for a doped polyaniline film (4.1
g/m2h),209 125 for a nylon–polyacrylic acid membrane
(5400 g/m2h), and 72 for a polysulfone.210 Pyridine can
be dehydrated with a membrane of a copolymer of acry-
lonitrile and 4-styrenesulfonic acid to give more than 99%
pyridine.211 A hydrophobic silicone rubber membrane re-
moves acetone selectively from water. A hydrophilic
cross-linked polyvinyl alcohol membrane removes water
selectively from acetone. Both are more selective than
distillation.212
Benzene can be separated over cyclohexane with an -
value of 26 with a polvinyl alcohol–poly(allylamine) blend
containing a cobalt(II) complex.213 An -value of 60 has
been obtained by pervaporation with a poly(acrylonitrile-
co-methyl methacrylate) membrane.214 Membranes of
porous polyethylene grafted with glycidyl methacrylate215
and poly(N,N-dimethylacrylamide-co-methyl methacry-
late)216 have also been used in this separation with separa-
tion factors of 21–22. This is a separation that would be dif-
ficult to do by size and by distillation. The two boil only
2°C apart. The cyclohexane produced by the reduction of
benzene is the starting material for nylon. The best solution
to the problem is to run the reduction to 100% completion.
Pervaporation can also be used to remove organic com-
pounds from wastewater. Elastomeric hydrophobic poly-
mer membranes are used to remove compounds more hy-
drophobic than acetone present at levels of 200–50,000
ppm.217 Compounds such as 2-butanone, benzene, and
trichloroethylene can be recovered. A polyphosphazene
–poly(dimethylsiloxane) graft copolymer membrane was
able to concentrate 7% ethyl acetate in water up to 97%.
The use of silicalite in poly(dimethylsiloxane) improves
both selectivity and flux rate.218
Chapter 7
Catalytic membrane reactors combine reaction and sep-
aration into a single step.219 They can result in a cheaper and
cleaner product that needs no further processing. The cata-
lyst can be on one side of the membrane (fluidized220 or not)
or actually in the membrane. The reaction product can be re-
moved as formed, as in the hydrolysis of a macromolecule,
for which an ultrafiltration membrane keeps the polymer in
the reaction vessel, but allows the hydrolyzate to pass. Per-
vaporation or a liquid passing by can be used to remove the
product. Continuous removal of a product can shift an equi-
librium in the desired direction, as in dehydrogenations. It
can eliminate inhibition of cells by the products of their re-
action. By this process, unwanted secondary reactions of the
primary products can be eliminated or reduced. Sometimes
a membrane can prevent poisons from getting to a catalyst.
Membranes can allow slow, steady addition of a reagent to
avoid locally high concentrations that could lead to hot
spots. One reactor design uses mixing spheres in microp-
orous tubes to eliminate hot spots and improve yields.221 A
few examples will be given to illustrate the diversity of re-
actions that can be run in membrane reactors. Many more
can be found in the foregoing review references.
Removal of hydrogen through membranes has im-
proved conversions and yields in some dehydrogena-
tions.222 The dehydrogenation of n-butane in a Pd/Ag
membrane reactor increased conversions four-4 to sixfold
over equilibrium values.223 Conversions were up 1.5 times
when a polyimide membrane was used.224 One problem
has been to obtain a high enough permeation rate of hydro-
gen through dense palladium membranes. To raise the flux
rate, very thin layers of palladium have been placed on tan-
talum and niobium225 or on porous ceramics.226
Ethylene and acetaldehyde are the main products when
carbon monoxide is reduced by hydrogen permeating
through a membrane of palladium.227 The main products
are methane and methanol when a supported palladium cat-
alyst is used, instead of the membrane. Cyclododecatriene
was reduced with hydrogen to cyclododecene with 88% se-
lectivity at 96% conversion, and with 80% selectivity at
100% conversion, using a membrane with palladium in the
pores of alumina.228 A microporous ceramic membrane
containing titanium dioxide and platinum was used in the
reduction of 2-hexyne to cis-2-hexene with hydrogen, with
100% selectivity.229 Vegetable oils reduced with hydrogen
in a tubular ceramic membrane reactor with palladium in
the membrane gave a product with 2–5% trans-content,
about three to four times lower than in a conventional
slurry reactor.230 (trans-Fatty acids cause as much heart
disease as saturated fats.)
Ceramic membranes of mixed oxides, formed by heating
mixtures of lanthanum, strontium, cobalt, and iron carbon-
Chemical Separations
ates or nitrates, allow oxygen, but not nitrogen, to pass.231
This eliminates the need for an air separation plant. Such a
membrane reactor was used to oxidize methane to carbon
monoxide with 90% selectivity at 98% conversion.232 This
process is 25% cheaper than the usual method of making
synthesis gas from natural gas.233 Yttria-stabilized zirconia
also permeates oxygen selectively over nitrogen, but the flux
rate is lower.234 The highest oxide ion mobility known is that
of cubic Bi2O3 electrodeposited on gold.235 The yield of C2
compounds has been improved by feeding methane and oxy-
gen on opposite sides of a mixed barium, cerium, and
gadolinium oxide membrane.236 The best selectivity was
70% at 8% conversion with the membrane, compared with
32% selectivity without it. The selectivity to C2 products
was 94% with a Y2O3 /Bi2O3 membrane at higher than
800°C.237 With a Mn/Na2WO4 /SiO2 membrane, the product
contained 30% ethane, 40% ethylene, and 10% propylene at
20% conversion.238 Another group obtained 85% selectivity
to coupled products using a membrane reactor of Sr, La, and
Bi oxides with silver on a yittria-stabilized zirconia tube.239
A better solution to this problem of making C2 compounds
is to make the ethylene by dehydration of ethanol from fer-
mentation. (For making monomers and other materials from
renewable sources, see Chap. 12. This will help moderate
global warming, as described in Chap. 15.)
The exotherm from the reaction of sulfur trioxide with
toluene can be moderated by feeding the sulfur trioxide
through a tube with 0.5-m pores.240 Iron phthalocyanine
can be prepared in the cages in sodium Y zeolite. This is then
protected by a cover of cross-linked poly(dimethylsiloxane).
Cyclohexane on one side of this membrane has been oxi-
dized by tert-butylhydroperoxide on the other at room tem-
perature to a 95:5 mixture of cyclohexanone and cyclohex-
anol at 25% conversion.241 The zeolite protected the catalyst
from oxidation.242 The membrane could be regenerated by
washing with acetone and drying. This reaction is of interest
because the oxidation of cyclohexane is used to make ny-
lons. The challenge is to use a membrane reactor with oxy-
gen to obtain high conversions to these products. Continuous
separation of the products through a membrane might help.
7.34
191
Chiral catalytic membranes have been prepared by oc-
cluding homogeneous ruthenium rhodium and manganese
catalysts in a polymerizing mixture that leads to a cross-
linked poly(dimethylsiloxane) rubber.243 The ruthenium
catalyst was used to reduce methyl acetoacetate with up to
70% enantioselectivity and the rhodium one gave 90% ee.
The manganese catalyst was used with styrene on one side
and aqueous sodium hypochlorite on the other to produce
the epoxide with 52% ee. The ruthenium and manganese
catalysts were used three times, with no loss of activity or
enantioselectivity. This appears to be a satisfactory way to
heterogenize homogeneous catalysts.
Continuous membrane bioreactors can have advan-
tages. One is the removal of inhibition of cells by the
product. This was shown in the oxidation of naphthalene
(7.34) by Pseudomonas fluorescens.244 An ultrafiltration
membrane kept the cells and insoluble naphthalene on one
side, while the soluble product was removed continuously
from the other. The yield was three times that in a batch
process.
Inhibition of animal cell cultures by ammonia has been
overcome by either passing oxygen through a porous
poly(tetrafluoroethylene) membrane into the culture or by
continuous removal through a membrane of the same ma-
terial (0.2-m pores) to aqueous phosphoric acid on the
other side.245 Urea was removed by an anion-exchange
membrane clamped over an insolubilized polyvinyl alcohol
membrane containing urease.246 No ammonium ion
returned back into the feed solution. A urease in poly(ethy-
lene-co-vinyl acetate) converted urea on one side to
ammonia for recovery on the other.247
A cheaper process for the environmentally friendly sol-
vent ethyl lactate uses a membrane to separate ammonia
and water by-products. The ammonium lactate made by
fermentation of carbohydrates is cracked to lactic acid,
which is then esterified with ethanol. This process elimi-
nates the large amounts of waste salts formed with other
processes.248 This solvent has been suggested as a replace-
ment for 80% of the 3.8 million tons of solvent used each
year in the United States for electronics, paints, coatings,
textiles, cleaning, adhesives, printing, and deicing.
192
A membrane cell recycle reactor with continuous
ethanol extraction by dibutyl phthalate increased the pro-
ductivity fourfold with increased conversion of glucose
from 45 to 91%.249 The ethanol was then removed from
the dibutyl phthalate with water. It would be better to do
this second step with a membrane. In another process, mi-
croencapsulated yeast converted glucose to ethanol,
which was removed by an oleic acid phase containing a li-
pase that formed ethyl oleate.250 This could be used as
biodiesel fuel. Continuous ultrafiltration has been used to
separate the propionic acid produced from glycerol by a
Propionibacterium.251 Whey proteins have been hy-
drolyzed enzymatically and continuously in an ultrafiltra-
tion reactor, with improved yields, productivity, and elim-
ination of peptide coproducts.252 Continuous hydrolysis of
a starch slurry has been carried out with -amylase im-
mobilized in a hollow fiber reactor.253 Oils have been hy-
drolyzed by a lipase immobilized on an aromatic
polyamide ultrafiltration membrane with continuous sepa-
ration of one product through the membrane to shift the
equilibrium toward the desired products.254 Such a pro-
cess could supplant the current energy-intensive industrial
one that takes 3–24 h at 150–260°C. Lipases have also
been used to prepare esters. A lipase–surfactant complex
in hexane was used to prepare a wax ester found in whale
oil, by the esterification of 1-hexadecanol with palmitic
acid in a membrane reactor.255 After 1 h, the yield was
96%. The current industrial process runs at 250°C for up
to 20 h.
Some oxidoreductases require expensive cofactors,
such as NADH. This requires continuous regeneration of
the cofactor in a separate enzymatic reaction using a sacri-
ficial substrate. Nanofiltration membranes have been used
to separate the two enzyme systems.256 A sulfonated poly-
sulfone nanofiltration was used in the reduction of fructose
to mannitol, using glucose to gluconolactone to regenerate
the NADH.
The use of membrane reactors can be expected to ex-
pand dramatically in the future. The search for improved
selectivity, permeability, stability and resistance to fouling
of membranes will continue.
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1. (a) N.N. Li, ed. Separation and Purification Technology,
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(b) S.D. Barnicki, and J.J. Siirola. Kirk–Othmer Encyclo-
pedia of Chemical Technology, 4th ed. 1997,
21:923–962.
(c) J.D. Seader, and E.J. Henley. Separation Process Prin-
ciples. Wiley, New York, 1998.
Chapter 7
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248. (a) G. Parkinson. Chem Eng 1998, 105(4):27.
(b) L.R. Raber Chem Eng News July 6, 1998, 25.
249. H.N. Chang, J.W. Yang, Y.S. Park, D.J. Kim, and H.O.
Han. J Biotechnol 1992, 24:329.
250. A.C. Oliveira, and J.M.S. Cabral. J Chem Technol
Biotechnol 1991, 52:219.
251. P. Boyaval, C. Corre, M–N Madec. Enzyme Microb Tech-
nol 1994, 16:883.
252. A. Perea and U. Ugalde. Enzyme Microb Technol 1996,
18:29.
253. Y–H. Ju, W–J. Chen, and C–K. Lee. Enzyme Microb
Technol 1995, 17:685.
254. R. Molinari, M.E. Santoro, and E. Drioli, Ind Eng Chem
Res 1994, 33:2591.
255. Y. Isono, H. Nabetani, and M. Nakajima. J Am Oil Chem
Soc 1995, 72:887.
256. (a) B. Nidetzky, D. Haltrich, K.D. Kulbe. Chemtech 1996,
26(1):31.
(b) D. Gollhofer, B. Nidetzky, M. Fuerlinger, and K.D.
Kulbe, Enzyme Microb Technol 1995, 17, 235.
200
RECOMMENDED READING
1. A. Johansson. Clean Technology. Lewis Publishers, Boca
Raton, Florida. 1992:109–125.
2. L.P. Raman, M. Cheryan, N. Rajagopalan. Chem Eng Prog
1994; 90(3):68.
3. A. Shanley. Chem Eng 1994, 101(9):34.
4. P. Cartwright. Chem Eng 1994, 101(9):84.
5. E. Driolo, L Giorno. Chem Ind (London) 1996:19.
6. R. Singh. Chemtech 1998, 28(4):33.
7. G. Karet R&D (Cahners) 1999, 41(3):35.
8. For a more detailed review see, RW Baker Kirk–Othmer En-
cyclopedia of Chemical Technology 4th ed. 1995, 16:135.
EXERCISES
1. If you have never used a membrane for a separation,
have one of the biochemists near you show you how
it is done.
2. Think of the most difficult separations you have
done. Could any of them have been performed more
easily by using the methods outlined in this chap-
ter?
3. Design a ligand for gold that will allow recovery of
the metal from ores without the use of cyanide ion.
Chapter 7
4. If you have never made an inclusion compound,
look up the separation of a long-chain aliphatic
compound with urea and try it in the laboratory.
5. Reactive distillation and catalytic membrane reac-
tors separate products of reactions before secondary
reactions can occur. Think of some places where
they can be applied to favor mono-, rather than di-
additions or substitutions.
6. Look up the dimensions and coordinating ability
of some common ions that are difficult to separate
from others. Compare these with the dimensions
and conformations of typical crown ethers,
cryptands, and calixarenes. Then extrapolate
the data to the design of a new highly selective
reagent.
7. Think of a difficult separation of small organic
molecules. Match the sizes with those of the cavi-
ties of hosts that might allow a separation by the
formation of an inclusion compound.
8. Compare the selectivity of the best synthetic mem-
branes and ligands for separating ions with the
specificities that are achieved by biological mem-
branes. How might we mimic the biological mem-
branes more successfully?
8
Working Without Organic Solvents
I. ADVANTAGES AND DISADVANTAGES
OF SOLVENTS
Solvents are very useful. They can be used to1
1. Place reagents into a common phase where they
can react
2. Dissolve solids so they can be pumped from place
to place
3. Lower viscosity and facilitate mixing
4. Regulate temperatures of reactions by heating at
reflux
5. Moderate the vigor of exothermic reactions
6. Allow recovery of solids by filtration or centrifu-
gation
7. Extract compounds from mixtures
8. Purify compounds by recrystallization
9. Convert pyrophoric materials to nonpyrophoric
solutions (as for aluminum alkyls)
10. Remove azeotrope compounds from reactions
11. Clean equipment and clothing
12. Place a thin film of material on to a substrate
The United States uses 160 billion gal of solvent each
year.2 The largest single use is for vapor degreasing, fol-
lowed by dry cleaning, then by immersion cleaning of
parts.
The disadvantages of solvents include the following:
1. Loss of 10–15 million tons of solvents (with a fuel
value of 2 billion dollars) each year 3
2. Reaction of lost solvents in air with nitrogen oxides
in sunlight to produce ground level ozone
3. Destruction of upper atmosphere ozone by
chlorofluorocarbons
4. Toxicity of chlorinated and other solvents to
workers
201
5. Miscarriages caused by ethers of ethylene glycol
6. Birth defects from exposure to solvents4
7. Fires and explosions may result from use
8. Monetary cost
Large point sources can account for much loss of sol-
vents. For example, the largest sources in Delaware (see
Chap. 1 for a table of sources) are the painting of cars in
two auto assembly plants. Nonpoint and smaller sources
often produce more total emissions than the large sources.
Delaware violates the Clean Air Act for ground level ozone
several times each year, largely because of too many cars.
There are many smaller commercial sources of solvent
emissions, including dry-cleaning shops, printing estab-
lishments, metal-cutting fluids in machine shops, auto
body repair shops, and many others. The consumers also
emit solvents from their homes when they use paint re-
mover, oil-based paints, adhesives, spot remover, charcoal
lighter fluid, aerosol cans of personal care products, hair
spray, nail polish, and gasoline-powered tools, among
many. The use of chlorinated solvents minimizes the risk of
fire, but causes toxicity problems, such as liver damage and
cancer. If other volatile solvents are used, all equipment in
the plant must be explosion-proof, which includes placing
every electrical switch in a heavy metal container. The lim-
its being set on these volatile organic compound emissions
(VOCs) from various products are the subject of some con-
troversy in the United States.5
A tiered approach to this problem from the least change
to the most change might be the following:
1. Place something on the plant outlet to destroy or re-
cover the solvent
2. Enclose the operation so that the solvent is not lost
(see Chap. 3 for low-emission degreasing in a
closed system)
202
3. Substitute a less harmful solvent
4. Use supercritical carbon dioxide as a solvent
5. Use water
6. Use no solvent
7. Switch to another process that eliminates the need
for the solvent
8. Can we do just as well without the product made
with the solvent?
For laboratory use and, perhaps, for small-volume produc-
tion, another first stage can be added. Microreactors, which
require much less solvent, are being studied for fluorina-
tion,6 DNA chips, and other uses.7 A variation on item 2 is
the use of a polyhydroxyester based on aromatic epoxy
resins and aliphatic carboxylic acids to reduce the loss of
styrene from unsaturated polyester resins by 95–99%.8
Various methods are used for the recovery or destruc-
tion of solvent emissions.9 Reichhold Chemical in Dover,
Delaware, has added a gas-fired incineration unit to destroy
emissions of 1,3-butadiene and acrylonitrile.10 The energy
use in such systems tends to be high. The energy use and
the temperature can occasionally be reduced with cata-
lysts.11 In some cases the air containing the solvent can be
run into the plant boiler. If the amount of the volatile or-
ganic compound is low, a biofilter may be suitable for re-
moving it. Capitol Cleaners, a family-owned dry cleaning
business in Dover, Delaware, has reduced its use of per-
chloroethylene by 96%, through the use of new tighter
equipment and a system that filters and redistills used sol-
vent. The pay-back period for the investment was 4 years.12
Dow has designed closed system equipment for the use of
chlorinated solvents.13 Solvent emissions can also be re-
covered for reuse by adsorption and by refrigeration.14 If a
large volume of air is used to keep the levels of solvents in
the air of the plant low, then cold traps are not particularly
effective. If the concentration of the organic compound in
the air is higher than 1%, recovery by membranes (see
Chap. 7) may be possible.15
Recovery of used solvents by distillation, on site or off
site at a central facility, is much easier if each solvent is
stored separately. A single solvent for the whole plant
would be desirable if a solvent must be used. Sandoz
Pharmaceutical (now Novartis) has done this for a pro-
cess, with the result that they now produce only 1.5 lb of
waste per pound of product instead of the former 17.5
lb.16 For an investment of 2.1 million dollars, they save
775,000 dollars/year. Processes that use solvent mixtures
should be restudied to see if a single solvent can be used
instead. Solvent recovery almost never reaches 100%. A
plant extracting oil from soybeans recovered 99.92% by
use of desolventizer toasters with fully countercurrent
stripping steam.17 It still lost 0.3 gal solvent per ton of
Chapter 8
beans. It is hard to extract the last traces of solvent from
a viscous polymer. If supercritical carbon dioxide extrac-
tion were used, the amount left in the beans would not
matter. This is a big improvement over an incident that
happened a few years ago in Louisville, Kentucky, in a
similar plant. Hexane lost from the plant seeped into the
sewer beneath a local street. A spark from a passing car
that backfired ignited the hexane, causing the street to
blow up.
Various substitutes have been suggested for the objec-
tionable solvents.18 Alkanes and alcohols produce much
less ground level ozone than equal amounts of alkenes and
aldehydes.19 Toluene and 2-butanone produce less than the
xylenes. Ferro Corporation is selling Grignard reagents in
the dibutyl ether of diethyleneglycol (butyl diglyme),
which it says is a safer solvent owing to its higher boiling
point and lower solubility in water than the usual ether sol-
vents.20 duPont is marketing a mixture of dimethyl succi-
nate, dimethyl glutarate, and dimethyl adipate, a by-prod-
uct of making nylon (see Chap. 1), as a less toxic solvent.21
Monsanto sells a similar mixture.22 Eastman says that its
diethoxymethane can be used as a replacement for tetrahy-
drofuran, methylene chloride, and the dimethyl ether of
ethylene glycol.23 tert-Butyl methyl ether can be used as
a replacement for 1,2-dimethoxyethane, 1,4-dioxane,
methylene chloride, and tetrahydrofuran.24 Its solubility in
water is small so that the workup of a reaction can involve
addition of water. N-Methylpyrrolidone is a low-toxicity
solvent that can be used to clean silicon chips.25 Toxic
hexamethylphosphoramide can be replaced by 1,1,3,3-
tetramethylguanidine in reactions with samarium(II)
iodide.26 “Methyl siloxane fluids” [probably poly(dime-
thylsiloxane) oils] have been suggested as alternatives to
chlorofluoroarbons for precision cleaning.27 Methyl soyate
(the methyl ester of soybean fatty acids) is being sold as a
replacement for trichloroethylene used in cleaning metal
parts.28
Perfluorohexane has been used as a replacement for car-
bon tetrachloride in brominations and as a “universal”
medium for suspension polymerization.29 It can be used
with monomers that contain water-sensitive groups, such
as isocyanate, chlorocarbonyl, and trimethoxysilyl. Perflu-
orotriethylamine has been used as a solvent for Lewis acid-
catalyzed reactions.30 Oxychem sells 4-chlorobenzotrifluo-
ride as a solvent. Benzotrifluoride itself has been used as a
substitute for methylene chloride.31 Before these materials
are used on a large scale, their potential as greenhouse
gases should be checked. As mentioned in Chap. 3,
tetrafluoromethane is a very potent greenhouse gas. Ethyl
lactate and propyleneglycol ethers have been suggested as
replacements for ethyleneglycol ethers used by the semi-
conductor industry.32 The use of 1-butyl-3-methylimida-
Working Without Organic Solvents
zolium hexaflorophosphate and other ionic liquids33 to
replace organic solvents was described in Chap. 7.
Progress in using carbon dioxide or water as solvents, as
well as reactions performed without solvent will now be
examined. These approaches are better than simply substi-
tuting another organic solvent for the objectionable one.
There are also some applications for which the use of sol-
vent-containing materials can be avoided by choice of
other systems. If a building is made of wood, it has to be
painted, often with an oil-based paint. If it is covered with
brick, stone, stucco, aluminum, or poly(vinyl chloride, no
painting is needed. A room covered with wallpaper (put up
with an aqueous adhesive) does not need to be painted.
Wash-and-wear garments do not have to be dry cleaned. If
a nail polish free of solvents cannot be devised, it will not
be a big problem for society.
II. WORKING WITHOUT SOLVENT
Many industrial processes for making commodity chemi-
cals are carried out in the gas phase without solvent using
heterogeneous catalysts. For example, methanol is made
from synthesis gas (a mixture of carbon monoxide and hy-
drogen) using zinc oxide-containing catalysts.34 The heat
of the exothermic reaction is moderated by injecting cold
synthesis gas at several places in the reactor. Oxidation of
methanol to formaldehyde with oxygen is done in the gas
phase, with an excess of methanol to keep outside the ex-
plosive limits. Water is used in the mixture to moderate the
heat evolved. In some reactions, carbon dioxide is used as
the inert heat-moderating gas. Fluorinations can be con-
trolled by adding the fluorine in a dilute nitrogen stream.
Ethylene and propylene can be polymerized in the gas
phase using fluidized bed techniques.35 Bayer uses a
neodymium catalyst for the fluidized gas-phase polymer-
ization of 1,3-butadiene in a new process that uses 50% less
energy and costs 30% less.36 Hydrocarbon solvents were
formerly used for these processes. Propylene is also poly-
merized as a liquid without solvent. Showa Denko has a
process for the oxidation of ethylene in the gas phase to
8.1
203
acetic acid using a palladium catalyst.37 It produces one-
tenth as much effluent as the process for making acetalde-
hyde in solution. Arylacetonitriles can be methylated in the
gas phase at 180°C, using gas–liquid phase-transfer cataly-
sis with a film of a potassium carbonate-containing
polyethylene glycol on corundum (a form of aluminum ox-
ide) spheres (8.1).38
K2CO3
ArCH2CN  CH3OCOOCH3  →
CH3

ArCHCN  CO2  CH3OH (8.1)
99% conversion
99.5% selectivity
The nontoxic dimethyl carbonate replaces the highly toxic
cancer-suspect dimethyl sulfate and iodomethane normally
used in methylations. The by-product methanol can be con-
verted to more dimethyl carbonate by oxidative carbonyla-
tion. The only waste is nontoxic carbon dioxide. (See Chap.
2 for more detail on reactions of dimethyl carbonate.)
General Electric has replaced the methylene chloride
used in recrystallizing bisphenol A with a fractional,
falling-film, melt crystallization.39 This simplified system
has saved energy at the same time that it has eliminated
drying and distillation steps. The mechanical extraction of
soybeans does not remove quite as much oil as extraction
by hexane, but the press cake is a higher-energy animal
feed.40 This can also be done in an extruder with a resi-
dence time of 30 s at 135°C.41 The pressed oil commands a
higher price in niche markets.
There are times when excess starting material can serve
as the solvent. Excess liquid chlorine has been used in the
chlorination of natural rubber to eliminate the need for the
usual carbon tetrachloride.42 It is difficult to remove the
last traces of carbon tetrachloride from the chlorinated rub-
ber. The dimethyl terephthalate and terephthalic acid used
in the preparation of poly(ethylene terephthalate) (8.1) are
made by the oxidation of p-xylene.43
204
8.2
The dimethyl terephthalate is recrystallized from the
starting material, p-xylene. The terephthalic acid is recrys-
tallized from water at 225–275°C.
Many reactions can be carried out without solvent when
the reagents are liquids or when the mixture can be melted
to produce a liquid.44 This includes cases in which a solid
reagent gradually dissolves in the other as the reaction pro-
ceeds. Esters of rosin are made in melts, which solidify on
cooling. Rosin is a mixture of resin acids obtained from
pine trees. The one shown, abietic acid, can be esterified
with pentaerythritol (8.2) as shown, or with other alcohols.
The current literature contains many reactions that are
run without solvent. Frequently, this can offer improved
yields and selectivity as well as simplicity. Almost all of
them still use solvents in the workup and sometimes involve
chromatographic separations. This solvent might be
avoided by filtering off a solid catalyst, then using it in the
next run without washing it with solvent to recover the last
of the product. Other possibilities include distillation under
vacuum, extraction with supercritical carbon dioxide, and
extraction with water plus or minus a hydrotropic agent,
possibly at high temperature. (Some of these are discussed
later.) If the reaction has been run on a solid support, dis-
placement of a less polar product by a more polar starting
material (as in the oxidation of an alcohol to a ketone) may
be possible. The goal is to find simple, convenient, fast,
energy-efficient ways to isolate the product and to recycle
any catalysts and supports. If the product is obtained in
100% yield at 100% conversion no further treatment will be
needed. In the much more likely case that unreacted starting
8.3
Chapter 8
materials and by-products are present, the product will have
to be obtained by distillation, membrane separation, or other
means. A few examples will illustrate the possibilities.
Varma has run many types of reactions on nontoxic sup-
ports, such as alumina, silica, and clay, using microwaves.45
(For more on the use of microwaves, see Chap. 15.) The
method offers selectivity under safe, fast, mild reaction con-
ditions in open vessels. The supports can be recycled. The
reactions include oxidations, reductions, nitrations, aldol
condensations, and others. Solvents were used in the
workups. Other workers have devised a condensation (8.3)
of aromatic aldehydes with malonic acid (without a support)
that uses no solvents at all.46 The workup consisted of pour-
ing the glassy reaction mixture from the Erlenmeyer flask
into ice water, filtering off the solid, and drying it. The con-
ventional procedure for this reaction requires heating at
120°C for 3 h to give the product in 96% yield.
Aldehydes can be condensed with aliphatic nitro com-
pounds (8.4) using an ion-exchange resin47 or a potassium-
exchanged–layered zirconium phosphate as a catalyst.48
8.4
Working Without Organic Solvents
8.5
The yields were 62–89%. The ion-exchange resin and
the zirconium phosphate were washed with hazardous
methylene chloride to recover the products. The catalyst
could be reused with little loss in activity.
Michael additions of -diketones to -, -unsaturated
ketones can be run without solvent with the help of mi-
crowave radiation (8.5) to give the adducts in 63–95%
yields.49 Cerium(III) chloride can also be used. No poly-
merization of the methyl vinyl ketone takes place.
A condensation and reduction have been combined in
the preparation of methylisobutylketone from acetone
(8.6).50
For a reaction run at 160°C for 2 h, the selectivity to
methylisobutylketone was 92.5% at 46% conversion. The
by-products were 0.6% isopropyl alcohol and 3.6% di-
isobutylketone. The activity and selectivity remained con-
stant for 1500 h.
2-Hydroxypyridine has been N-alkylated (as the pyri-
done) with benzyl chloride (8.7) quantitatively without sol-
vent.51 However, methylene chloride was used in the
workup.
8.6
8.7
205
Some reactions can be quite exothermic. Before running
a reaction without solvent, it would be best to check the
heat of reaction by thermal analytical methods. This will
avoid runaway reactions. A thermoregulator should also be
used to control the temperature.
Some reactions can be run in the solid state with the aid
of ultrasound, grinding, heat, host–guest complexes, and so
forth.52 These include Michael reactions, Baeyer–Villiger
reactions, benzylic acid rearrangements, etherifications,
and others. Calix[4]arene (MP 310°C) can be converted to
its p-isopropyl derivative (8.8) by grinding it with a nickel
sulfate on alumina catalyst, heating to 210°C, then intro-
ducing propylene for 6 h.53 Chloroform was used in the
work-up. This procedure resolved the problem of the low
solubility of the starting material under the usual alkylation
conditions.
Thionocarbamates (8.9) have been made by grinding the
ingredients together with a mortar and pestle at room tem-
perature in air.54
The Friedel–Crafts alkylation of benzene with isopropyl
bromide (8.10) was run by grinding the ingredients in an
206 Chapter 8

8.8

8.9

8.10
Working Without Organic Solvents
8.11
agate mortar for 45 min, pouring onto crushed ice, and ex-
tracting with ether.55
The more environmentally benign solid acid Cs2.5H0.5
PW12O40 has been ground in a mortar with a diol for 5 min,
then left 9 h at room temperature to give the pinacol rear-
rangement (8.11).56
Solvents can be eliminated from some reactions by run-
ning them in ball mills.57 Methyl methacrylate can be poly-
merized in a vibratory ball mill using a talc catalyst.58 Ball
mills are feasible for reactions on a commercial scale. Huge
mills are used by the mining industry in grinding ores be-
fore flotation. If the mill is used repeatedly to make the
same product, the problem of cleaning it out between runs
is eliminated. It is also possible to use an inert liquid dilu-
ent in the milling, so that the product can be recovered as a
slurry. The preferred diluent would be water if it is inert for
the reaction in question.
Films of polyimides have been made (8.12) without sol-
vent by vapor deposition of the diamine and dianhydride on
to a cold surface, followed by heating.59 The films were
equivalent to those made from solution.
Inorganic compounds can also be made by solid-state
8.12
207
synthesis.60 The reactions are essentially controlled explo-
sions. Two of these reactions (8.2) are shown:
TiCl3  Li3N → TiN  3 LiCl
(8.2)
Fe2O3  Al → Al2O3  Fe
The analyses of traces of aromatic solvents and pesti-
cides in water can now be made without the customary sol-
vent extraction.61 The materials are extracted on to a fine
silica fiber coated with poly(dimethylsiloxane), on a poly-
acrylate, or on Parafilm. The samples are then desorbed
thermally in the inlet of the gas chromatograph, or with
Parafilm, just examined by infrared light.
III. REACTIONS IN EXTRUDERS
Extruders are in common use for the processing of poly-
mers, as in the spinning of synthetic fibers. They are also
used for the extrusion cooking of foods, such as ready-to-
eat breakfast cereals. They are not part of the standard
equipment of the usual chemical laboratory, yet they offer
considerable promise for running reactions without solvent
on a continuous basis.
208
An extruder is essentially a pipe with a small hole at one
end. Materials are put in at one end, as from a hopper,
pushed through by screws until they exit from the other
end. Twin intermeshing screws can give good mixing.62
Laboratory extruders can offer a variety of options. They
may have zones heated to different temperatures, inlets at
varying points along the tube where materials can be
added, vents that allow volatile substances to exit, and a va-
riety of hole sizes and shapes at the end. Thus, it is possible
to melt one material, add a reagent later, and take off a
volatile by-product farther down the barrel. The reaction
time can be varied by the screw speed and the length of the
barrel. The feed material can be blanketed with an inert gas,
such as nitrogen, if needed.
Polymerization is often incomplete. Traces of residual
monomer may adversely affect the properties of the poly-
mer, such as lowering the glass transition temperature (the
temperature at which a rubbery material becomes glassy).
Residual monomer is very undesirable if it is a carcinogen
such as acrylonitrile or vinyl chloride. Polymers for use in
contact with food must not lose a toxic monomer into the
food. Solvents and monomers are very difficult to remove
completely from polymers, but can be removed in a vented
extruder. Residual methyl methacrylate can be removed
from poly(methyl methacrylate) in a vented extruder.63 The
molecular weights of polymers that are too large for the in-
tended application can be reduced by passage through an
extruder. The opposite can also be accomplished. The
molecular weights of polymers with amino or hydroxyl
groups can be increased by chain extension with blocked
diisocyanates, the blocking agent coming out the vent.
Poly(ethylene terephthalate) with carboxylic acid end
groups can be reacted with bis(oxazoline)s to increase the
molecular weight and improve the physical properties.64
Poly(methyl methacrylate) can be converted to
monomer for recycling by passage through a continuous
twin screw extruder at a little over 400°C.65 The 95% yield
of 95–99% purity compares favorably with the 60–80%
yield of 60–80% purity of the batch process, which is ten
times slower.
Biodegradable plates, knives, forks, and leaf bags can be
made by molding or extrusion of starch plasticized with
10% water.66 After use, the materials could be composted.
A mixture of benzylated wood and polystyrene can be ex-
truded easily.67 The properties of the product are compara-
ble with those of poly(styrene).
Most reactive extrusion has dealt with polymers that can
be difficult to handle by other techniques.68 Polymers can
be cross-linked, grafted with other monomers, and so on.
Extrusion cross-linking of polyethylene wire coating raises
the maximum temperature of use. Polypropylene degrades
in this process, but can be cross-linked successfully if mul-
Chapter 8
tifunctional acrylate monomers are included with the per-
oxide used in the process.69 Butyl rubber can be halo-
genated. Polyvinyl chloride can be reacted with sodium
mercaptides. Polymers containing ester or carbonate
groups can be transesterified.70 Polycarbonate and
poly(butylene terephthalate) can be melt-blended in the
presence of a titanium alkoxide catalyst.71 A small amount
of transesterification can make dissimilar polymers com-
patible, even though without it they would be incompatible.
Block copolymers have been prepared by melt-blending a
mixture of poly(ethylene terephthalate) with nylon 6 or ny-
lon 6,6.72 Transamidation can also take place when a mix-
ture of polyamides is run through an extruder.73
Coextrusion of L-lactide (a cyclic dimer lactone of lac-
tic acid) with hydroxy-terminated poly(caprolactone) in the
presence of stannous octoate gave a block copolymer.74
Block copolymers can also be used as compatibilizers for
the homopolymers, in addition to having interesting prop-
erties in their own right.75 Copolymers of ethylene and
vinyl acetate can be treated with methanol and a little
sodium methoxide to remove some of the acetate groups
from the copolymer.76 The by-product methyl acetate
comes out the vent of the extruder. n-Butyl alcohol can be
used in the same way.77 The product copolymer is useful as
a gas barrier coating on films for packaging food.
Graft polymerization in an extruder is used to alter the
properties of a polymer (e.g., make a polyolefin more polar
so that it can stick to more polar surfaces. This is another
way of making compatibilizers for dissimilar polymers.
Maleic anhydride can be grafted to polyethylene in an ex-
truder.78 The anhydride groups in the graft copolymer can
be reacted with a terminal group in a condensation polymer
to produce a compatibilizer.79 A polypropylene–maleic an-
hydride graft was reacted with a terminal amino group in a
polyamide (polycaprolactam) (8.13) by reactive processing
in an extruder.80 Blends of polypropylene and nylons offer
properties not available in either homopolymer.
The same technique can be used to dye a material that is
otherwise difficult to dye. An ethylene–propylene copoly-
mer rubber was reacted first with maleic anhydride, then
with an aromatic amine dye in an extruder to produce
a dyed rubber.81 Dye sites can also be inserted into poly-
olefins by grafting them with dimethylaminoethyl me-
thacrylate, using azo or peroxide catalysts in an extruder.82
N-Vinylimidazole has been grafted to polyethylene in an
extruder with the help of dicumylperoxide.83 The product
was mixed with an acrylic acid-modified polypropylene
and used to compatibilize polyethylene and polypropylene.
This could be helpful in the recycling of mixed polyolefins
from municipal solid waste. Recycling of cross-linked
(thermoset) polymers is more of a problem because they
cannot be remelted in an extruder. However, they can be if
Working Without Organic Solvents
8.13
thermally reversible cross-links have been used in their
preparation.84 These include polyurethanes, Diels–Alder
reaction products, and so on.
Glycidyl methacrylate has also been grafted to
polypropylene to insert an epoxy group for later reaction
with something else.85 The product was used for coupling
with carboxy-terminated poly(butylene terephthalate)
(8.14) in a twin-screw extruder.86
Glycidyl methacrylate has also been grafted to
polyethylene and to poly(ethylene-co-propylene) using
peroxides in extruders.87 The reactive group need not be
pendant. It can be part of a copolymer. Ethylene–methyl
acrylate copolymers and styrene–maleic anhydride copoly-
mers have been reacted with ammonia and with amines in
extruders.88
The extruder can be used for a variety of polymeriza-
tions even if no preformed polymer is present.89 These
include the continuous anionic polymerization of caprolac-
tam to produce nylon 6,90 anionic polymerization of capro-
lactone;91 anionic polymerization of styrene;92 cationic
copolymerization of 1,3-dioxolane and methylal;93 free
radical polymerization of methyl methacrylate;94 addition
of ammonia to maleic anhydride to form poly(succin-
imide);95 and preparation of an acrylated polyurethane
from polycaprolactone, 4,4-methylenebis(phenyl iso-
cyanate), and 2-hydroxyethyl acrylate.96 The technique of
reaction injection molding to prepare molded parts is
slightly different. Polyurethanes can be made this way by
8.14
209
injecting separate streams of diol and diisocyanate into the
mold. In the metathesis polymerization of dicyclopentadi-
ene,97 the procatalyst is put in one stream and the catalyst
activator in the other. The procatalyst is usually a tungsten
or molybdenum complex and the catalyst activator is a
metal alkyl. Polymerization is through opening the nor-
bornene double bond with cross-linking by opening some
of the cyclopentene double bonds (8.15). The monomer
usually contains a dissolved rubber to make the liquid more
viscous and to improve the impact strength of the molding.
Hydrogen has been used to reduce vegetable oils at
150°C in a twin-screw extruder coated with a palladium
catalyst.98 This continuous process with 20% conversion
per pass decreased catalyst consumption and eliminated a
catalyst separation step. However, the hydrogenation rate
was only one-tenth that when a palladium-on-carbon cata-
lyst slurry was used. It might be increased by putting more
catalyst on the extruder, by using a longer extruder barrel,
or by using the catalyst slurry method in an extruder.
These examples show that it is possible to handle gases
and liquids of low molecular weight in reactions in extrud-
ers. The presence of a polymer is optional. It is possible to
remove volatile by-products through a vent. The catalyst, if
any is needed, can be in a coating in the extruder. Viscous
mixtures are not a problem. A jacketed extruder can be
used to remove heat if necessary. Thus, it should be possi-
ble to run many of the usual reactions in extruders. The
only deterrents for the chemist in the laboratory might be
210
8.15
the need to work on a slightly larger scale and the increased
time to clean the extruder between runs. It is possible that
miniextruders exist or that the present ones can be scaled
down. This underused apparatus offers great potential for
the elimination of solvents.
IV. CARBON DIOXIDE AS A SOLVENT
Carbon dioxide is nontoxic, nonflammable, relatively inert,
abundant, and inexpensive. It does have some limitations.
It has to be used under pressure, and it is not a very good
solvent for many substances. As a solvent, it is used most
commonly as a supercritical fluid (i.e., above its critical
temperature of 31.1°C and critical pressure of 7.38 MPa).
In this region the density of the material and its solvent
power can be varied by changing the temperature and pres-
sure. The system has properties between those of gases and
liquids. Diffusivity and mass transfer are better than in liq-
uids, such as the usual organic solvents. The low critical
temperature allows heat-sensitive materials to be processed
without damage. Supercritical carbon dioxide (also written
sc carbon dioxide) is not the only supercritical fluid that
can be used, but it is among the few that offer the combi-
nation of properties given. Many have much higher critical
temperatures or are flammable. Several reviews are
available.99
That many chemical substances are not soluble in sc car-
bon dioxide permits selective extraction.100 It is often used
with foods, for which it eliminates the possibility of leav-
ing toxic residues of solvents such as methylene chloride.
It also avoids the hydrolysis that might occur when esters
(for flavors or fragrances) are recovered by steam distilla-
tion. It has been used to extract the flavor from hops, the
caffeine from coffee, fat and cholesterol from foods,101
pecan oil,102 lavender oil (for which hydrolysis of linalyl
acetate could occur in steam distillation),103 ginseng (from
which it does not extract pesticide residues),104 ginger,105
microalgae,106 cooked chicken,107 ethanol from cider,108
and many others. One method used with aromas and con-
Chapter 8
taminants in water is to pass the liquid through polypropy-
lene tubes immersed in liquid carbon dioxide.109 The addi-
tion of a few percent of a solvent such as ethanol or hexane
increases the number of things that can be extracted. The
addition of ethanol (a relatively nontoxic solvent) to the su-
percritical carbon dioxide has been used in the extraction of
oil from cottonseed,110 oil from sunflower seed,111 phos-
pholipids from canola oil,112 and antioxidants from the
seed coat of Tamarindus indica.113 By using sc carbon
dioxide, the oil content of seeds can be extracted for mea-
surement in minutes, compared with hours in a Soxhlet ex-
tractor.114 (Oil seeds have also been extracted with
aliphatic hydrocarbons, alkyl chlorides, alcohols, and wa-
ter.115) Mono-, di-, and triglycerides can be fractionated to
more than 90% purity with supercritical carbon dioxide.116
Salicylic acid (o-hydroxybenzoic acid) of 99% purity can
be obtained by extraction away from the much less soluble
p-hydroxybenzoic acid.117 The plastic contaminants in pa-
per for recycling can be removed (55–79%) using sc carbon
dioxide fortified with a little pentane or ethanol.118 Motor
oil can be recycled with a combination of sc carbon diox-
ide and a ceramic ultrafiltration membrane.119 The oil
passes through leaving the metal-laden residue behind. En-
vironmental samples for analysis (such as contaminated
soils) can be extracted with sc carbon dioxide.120 Super-
critical fluids can be used to regenerate porous adsorbents
at 50–60°C, which is an improvement over the 800°C used
in a furnace or the 150°C used with steam.121 Residual
monomers in a copolyester of glycolic and lactic acids can
be removed by extraction with sc carbon dioxide.122 It can
also be used with an anion-exchange resin to recover indole
continuously.123 This might be applied to coal tar. Super-
critical carbon dioxide has also been used to extract organic
compounds from ionic fluids, such as 1-butyl-3-methylim-
idazolium hexafluorophosphate, as a way of working up re-
actions in this medium.124
Heavy metal ions can be extracted with sc carbon diox-
ide containing chelating agents for them.125 Uranium can
be extracted from aqueous nitrates (such as might be ob-
Working Without Organic Solvents
tained by dissolving spent fuel rods) by putting 1–3% trib-
utyl phosphate in the carbon dioxide.126 A hydrocarbon
solvent, such as dodecane, is normally used in this process.
Such extractions work better if the chelating agent contains
many fluorine atoms to make it more soluble in the carbon
dioxide.127 A highly fluorinated dithiocarbamate allowed
recovery of up to 98% of mercury, lead, chromium, and
iron.128 Copper(II) has been extracted from aqueous solu-
tions with fluorinated -diketones in carbon dioxide.129
The ease of penetration of materials by supercritical flu-
ids offers a way of inserting something into them.130 Su-
percritical carbon dioxide has been used to insert biocides
into wood,131 polyethylene glycol into leather,132 and
monomers and initiators, for subsequent graft polymeriza-
tion, into polymers, such as polyethylene and bisphenol A
polycarbonate.133 Polymers swollen in this way are plasti-
cized by the carbon dioxide. Polystyrene film has been
made by drawing such a material.134 This is also a way to
foam the polymers by releasing the pressure in the same
way that some breakfast cereals are prepared.135 Extrusion
processing of foods from sc carbon dioxide has been con-
sidered for continuous making of bread, low-fat snacks,
and similar food.136 Highly oriented microfibrils of
poly(acrylonitrile) have been prepared by spraying a solu-
tion of the polymer in dimethylformamide into sc carbon
dioxide.137 Drugs have been microencapsulated by the
rapid expansion of sc carbon dioxide containing the drug
and poly(lactic acid).138 Microparticles of poly(methyl
methacrylate) and polystyrene have been prepared by
spraying solutions of the polymers in organic solvents into
liquid carbon dioxide.139 A coaxial nozzle can be used for
the preparation of microparticles of polymers.140 Mi-
croparticles of rare earth metal acetates have been prepared
by passing a solution in dimethyl sulfoxide into sc carbon
dioxide.141 Solutions of steroid drugs, such as proges-
terone, in sc carbon dioxide can be released through a mi-
cronozzle to produce 4.5-mm particles. These are finer than
the 7.5-mm particles from jet milling. This may be cheaper,
faster, and kinder to heat-sensitive compounds.142 It is pos-
sible that the preparation of regenerated cellulose fibers
from solutions in N-methylmorpholine-N-oxide might be
improved by spinning into carbon dioxide, instead of into
water, as currently done. This would make it easier to re-
cycle the solvent. If desired, foamed fibers for extra bulk
could be prepared in this way.
Most polymers are insoluble in sc carbon dioxide, with
the exception of highly fluorinated ones.143 Even so, some
perfluoropolymers, such as poly(tetrafluoroethylene), still
require temperatures of 200–300°C to bring them into so-
lution.144 Silicone polymers are also somewhat soluble.
Poly(dimethylsiloxane) has been fractionated into different
molecular weights using sc carbon dioxide at 70°C.145 A
211
variety of cationic and free radical-catalyzed polymeriza-
tions have been carried out in this solvent using special sur-
factants.146 An example is a block copolymer of styrene
and 1,1-dihydroperfluorooctyl acrylate, which can emul-
sify up to 20% of a hydrocarbon as core–shell type mi-
celles.147 (The polymerizations have been done primarily
by de Simone and co-workers.148) Some have involved the
use of perfluoroazo- and perfluoroperoxide initiators.
These include polymerization of methyl methacrylate,149
acrylic acid,150 butyl acrylate,151 styrene,152 divinylben-
zene,153 vinyl acetate, with or without ethylene.154 Methyl
methacrylate has also been polymerized in a biphasic sys-
tem of carbon dioxide and water to produce a stable latex
without a surfactant.155 Isobutylene has been polymerized
by a 2-chloro-2,4,4-trimethylpentane–titanium tetrachlo-
ride initiator.156 Vinyl ethers and oxetanes have been poly-
merized with initiators such as ethylaluminum dichloride
and boron trifluoride etherate, without incorporation of car-
bon dioxide into the polymers.157 The polymerization of
propylene oxide with a zinc glutarate catalyst gave a
copolymer of carbon dioxide.158 Cyclohexene oxide be-
haves similarly.159 Under other conditions propylene car-
bonate can be obtained in almost quantitative yield.160 (It is
a candidate for addition to diesel fuel to reduce particulate
emissions.) The oxidative polymerization of 2,6-
dimethylphenol to a polyether has also been performed in
sc carbon dioxide.161 The ring-opening metathesis poly-
merization of norbornene with ruthenium tosylate has been
carried out in carbon dioxide.162 The cis/trans-ratio could
be controlled by traces of methanol. Bisphenol A polycar-
bonate has been made in sc carbon dioxide.163 Many an-
ionic polymerizations may be difficult to achieve because
the anions would react with carbon dioxide.
Supercritical carbon dioxide is suitable as a medium for
reactions of small molecules as well, including hydrogena-
tion, hydroformylation, Diels–Alder reactions, amination,
alkylation, isomerization, oxidation, cyclizations, and oth-
ers, as well as inorganic and organometallic reactions.164
Free radical reactions, such as the oxidation of cumene
with oxygen to give cumene hydroperoxide and the bromi-
nation of toluene to produce benzyl bromide proceed
normally.165 This provides an alternative to the carbon
tetrachloride often employed in halogenations. Tetrahepty-
lammonium bromide was a satisfactory phase-transfer
catalyst for the reaction of benzyl chloride with solid potas-
sium bromide in sc carbon dioxide containing 5 mol%
acetone.166 The corresponding reaction with potassium
cyanide has been carried without the acetone.167 The
reaction of soybean oil with glycerol to produce mono-
glycerides proceeded smoothly in carbon dioxide.168 This
eliminated the alkali catalyst and gave a better conversion
to a lighter-colored product, with less odor. It might be pos-
212
8.16
sible to combine this reaction with the initial extraction of
the oil from the beans.
Jessop and co-workers have pointed out that homoge-
neous catalysis in supercritical fluids can offer high rates,
improved selectivity, and elimination of mass-transfer
problems.169 They have used a ruthenium phosphine cata-
lyst to reduce supercritical carbon dioxide to formic acid
using hydrogen.170 The reaction might be used to recycle
waste carbon dioxide from combustion. It also avoids the
use of poisonous carbon monoxide to make formic acid and
its derivatives. There is no need for the usual solvent for
such a reaction, because the excess carbon dioxide is the
solvent. If the reaction is run in the presence of dimethy-
lamine, dimethylformamide is obtained with 100% selec-
tivity at 92–94% conversion.171 In this example, the ruthe-
nium phosphine catalyst was supported on silica.
Asymmetric catalytic hydrogenation of dehydroaminoacid
derivatives (8.16) can be performed in carbon dioxide us-
ing ruthenium chiral phosphine catalysts.172
The solubility of the catalyst salt is improved by the use
of 3,5-bis(trifluoromethyl)phenylborate or triflate anions.
Unsaturated fatty acids can be reduced in the same way.173
Hydrogenations in sc carbon dioxide can be more selective
than in the gas phase while using 35 times less catalyst.174
Cyclohexene was reduced with hydrogen and a polysilox-
ane-supported palladium catalyst in in a continuous-flow
reactor in 95–98% yields. Epoxides, oximes, nitriles, alde-
hydes, ketones, and nitro compounds can also be reduced.
By varying the temperature, the products from the reduc-
tion of nitrobenzene can be selected from aniline, cyclo-
hexylamine, dicyclohexylamine, and cyclohexane. In the
8.17
Chapter 8
same way, acetophenone can be converted to 1-
phenylethanol, 1-cyclohexylethanol, or ethylcyclohexane.
Hydroformylation of propylene with carbon monoxide
and hydrogen can also be carried out in sc carbon dioxide
using a dicobaltoctacarbonyl catalyst.175 However, the
method appears to offer no advantage over carrying out the
reaction in water, as described in Chap. 1. It might offer ad-
vantages with higher olefins that are not soluble enough in
water to use it as a solvent. Olefins have been converted to
their epoxides with tert-butylhydroperoxide and vanadium,
titanium, or molybdenum catalysts with more than 99% se-
lectivity at more than 99% conversion.176 Oxidation of a
substituted cysteine with tert-butylhydroperoxide (8.17) in
sc carbon dioxide showed a pronounced pressure-depen-
dent diastereoselectivity, with up to 95% diastereoisomeric
excess, whereas conventional solvents gave 0% excess.177
Mesitylene underwent monoalkylation with isopropyl
alcohol (or propylene) with 100% selectivity at 50% con-
version using a polysiloxane-supported solid acid
catalyst.178
A combination of sc carbon dioxide and light has been
used in flow reactors to make some metal complexes not
possible by other methods, for example, cyclopentadi-
enylMn(CO)2(H2) and Cr(CO)5(ethylene).179 A man-
ganese hydride has been added to olefins in carbon diox-
ide.180 A zeolite in sc carbon dioxide selectively adsorbs
2,7-dimethylnaphthalene so that it can be separated from
the desired 2,6-dimethylnaphthalene.181 The latter is oxi-
dized to the dicarboxylic acid for conversion to a higher-
melting analogue of poly(ethylene terephthalate). A pil-
lared clay made in supercritical carbon dioxide had a higher
Working Without Organic Solvents
catalytic-cracking activity and selectivity than the usual
pillared smectite.182 Supercritical carbon dioxide is a better
medium than organic solvents for inserting large amounts
of guest into a pillared clay without contamination with or-
ganic solvent, as shown by intercalation of 4-aminoa-
zobenzene into a montmorillonite pillared with tetramethy-
lammonium ion.183 Supercritical carbon dioxide is also
used to dry aerogels, such as that from zirconium diox-
ide.184 This prevents loss of surface area by partial collapse
during drying.
Enzymes can also be used in sc carbon dioxide.185 A
Pseudomonas lipase immobilized on silica gel gave better
conversions and enantioselectivity in the acetylation of
racemic alcohols with acetic anhydride than when used in
organic solvents.186 The lipase-catalyzed esterification of
glycidol gave 83% enantioselectivity, which is as favorable
as when the reaction is run in organic solvents.187 An im-
mobilized lipase has been used in the ethanolysis of cod
liver oil.188 Another immobilized lipase has been used to
convert oleic acid to various esters.189 The use of a lipase
in sc carbon dioxide for analyses of fats in foods cuts sol-
vent use by 98%.190 Polyesters have been made enzymati-
cally in carbon dioxide.191
One of the limitations on the use of sc carbon dioxide as
a reaction medium has been the difficulty of getting sub-
stances dissolved or finely dispersed in it. Johnston and co-
workers have overcome this difficulty for bovine serum al-
bumin by making a microemulsion of water in carbon
dioxide using the fluorinated surfactant (8.3).192
CF3O[CF2CF(CF3)O]3CF2COO NH 4 (8.3)
The biological activity of the protein is not lost in the pro-
cess. The authors point out that “Carbon dioxide and water
are the least expensive and most abundant solvents on
earth.” This method has also been used to prepare
CO2/H2O microemulsions of inorganic compounds, such
as potassium permanganate and potassium dichromate.193
Such micellar systems have been used in hydroformyla-
tions, hydrogenations, and carbon–carbon bond-forming
reactions.194 Similar CO2/H2O micelles have been formed
using a hydrophilic dendrimer with a coating of perfluo-
roalkyl groups.195 These were used to extract a dye from
water into carbon dioxide. (Anionic dyes, i.e., xanthene
carboxylic acids such as fluorescein, have also been ex-
tracted from water at pH 1–6 with an amine dendrimer with
hexadecanoylamide groups on the surface [in a toluene so-
lution] without the use of carbon dioxide.196) It may be
possible to extend these approaches to other liquids that are
immiscible with carbon dioxide.
Supercritical carbon dioxide is also useful in a variety
of applications as a replacement for organic solvents.
Union Carbide markets a process for spray-painting in
213
which the level of emissions of volatile organic com-
pounds is reduced by 80%.197 Less paint has to be used
because the microatomization caused by the evaporation
of the carbon dioxide eliminates pinholes so that thinner
coatings can be used. It can be used as a replacement for
tetrachloroethylene in the dry cleaning of clothes.198 Mi-
cell Technologies sells the equipment for the process.
This process does involve high pressures, which may be a
disadvantage in neighborhood cleaning shops. If so, the
local cleaner could send the clothes to a central cleaning
facility. Water pollution can be avoided by dyeing cotton,
wool, and poly(ethylene terephthalate) fabrics in super-
critical carbon dioxide.199 The cotton and wool require a
pretreatment with a polyether that dissolves the dye and
swells the fibers. Energy is saved that would be required
to dry fabrics dyed in water. Any dye that does not stick
to the fabric can be reused in the next run. Textiles of
poly(ethylene terephthalate)–cotton can be sized and de-
sized in liquid carbon dioxide.200 This is also a good way
to put on fluoropolymers for abrasion resistance. Block
copolymers of tetrahydropyranyl, heptafluorobutyl, and
pentadecylfluorooctyl methacrylates have been used as
photoresists in microlithography.201 Photolysis in the
presence of triarylsulfonium or diphenyliodinium salts
produces acid that hydrolyzes the tetrapyranyl groups
making the image insoluble in supercritical carbon diox-
ide. Pulsed sc carbon dioxide containing less than 5%
propylene carbonate has been used to remove conven-
tional photoresists from silicon wafers.202 This replaces
the aqueous sulfuric acid or organic solvents used in con-
ventional processes. (Ozone in cold water has also been
used to do this without the carbon dioxide.203 This elimi-
nates the need for the propylene carbonate and the high-
pressure equipment, but the ozone is much more toxic.)
Supercritical carbon dioxide is being used to make im-
proved pigmented powder coatings and artifical bone, a
combination of calcium hydroxyapatite and a biodegrad-
able polymer.204
Hydroquinone can be monoalkylated cleanly with su-
percritical methanol at 350°C/120 bars for 1 h (8.18). Ani-
8.18
214 Chapter 8

Corrosion can be a problem, especially if a chlorine-con-

8.19
line can be monomethylated with 98% selectivity under the
same conditions (8.19).205
This is an alternative for some of the methylations with
dimethyl carbonate that were discussed in Chap. 2.
V. WATER AS A REACTION MEDIUM
Supercritical water, with or without oxygen or catalysts,
can be used to decompose organic waste materials.206
8.20
8.21
taining compound is decomposed. This may require that
the reactor be made of titanium. The corrosion can be re-
duced by the use of sodium carbonate.207 Use of this sys-
tem at 380°C reduced the content of polychlorinated
biphenyls in a sample from 20 mg/L to less than 0.5
g/L. Trichloroethylene, 1,1,1-trichloroethane, and
trichloroacetic acid were destroyed with 99.96% effi-
ciency at 450°C for 60 ss using 1.5% hydrogen peroxide
plus sodium bicarbonate.208 Sodium nitrate or sodium ni-
trite could be used in place of the hydrogen peroxide. Ni-
trates, ammonium hydroxide, and amines, all are con-
verted to nitrogen at 350–360°C. Emulsions of petroleum,
water, and solids can be broken by heating to 350°C. Su-
percritical water has been used to recover 2,4-diamino-
toluene from distillation residues from the manufacture of
2,4-toluenediisocyanate.209
The critical temperature of water is 374°C. This is too
hot for most organic compounds. However, exploratory
work has been done with supercritical and near critical
water.210 At 300°C the polarity and density of water ap-
proach those of acetone at room temperature. Cyclohex-
anol (8.20) can be dehydrated to cyclohexene in 85%
yield at 278°C in 18 h. Pinacol (8.21) can be rearranged
quantitatively at 275°C in 60 min. Quantitative ring open-
ing of 2,5-dimethylfuran (8.22) occurs at 250°C for 30
min. Acetals and esters (8.23) can be hydrolyzed under
such conditions.
Diaryl ethers are cleaved rapidly. Poly(ethylene tereph-
thalate) is cleaved at 300°C. Vegetable oils can be hy-
drolyzed in more than 97% yield with water in 15–20 min
at 260–280°C.211 The nitrile, amide, and ester groups in
various copolymers of butadiene and ethylene can be hy-
drolyzed to carboxylic acid groups with water at
250–300°C.212 Phenols can be alkylated with secondary
and tertiary alcohols in water at 250–350°C, but the reac-

8.22

8.23
Working Without Organic Solvents
8.24
tion is slow.213 These reactions have no catalysts and no
solvent, so that there is no need to recover either. Many
products separate on cooling. Alkynes can be trimerized to
the corresponding aromatic compounds with cyclopentadi-
enylcobaltdicarbonyl in more than 95% yields.214
Not all yields are as good as those just quoted. The
yields of the desired olefin in the Heck reaction (8.24) are
only about 25%, several other products being formed at the
same time.215
Methacrylic acid, which normally is derived from
petroleum, can be made from citric acid (8.25) which in
turn is made by fermentation of glucose.216
The combined yield of itaconic and citraconic acids (in
about 3:1 ratio) in the first step was over 90%. The two in-
terconvert rapidly. Decarboxylation of the itaconic acid
gave methacrylic in 70% yield. Inclusion of 3-hydroxy-2-
methylpropionic acid as product raised the yield to over
8.25
8.26
215
80%. D-Glucose can be converted to D-erythrose (8.26) in
50% yield using water at 400°C for 0.11 s.217
Water at 250–300°C can remove organic compounds
from soil, catalysts, and some sludges, just as effectively as
organic solvents do.218
Water promotes many reactions at temperatures no
higher than 100°C.219 These include the Diels–Alder,
Heck, Michael, and Mukaiyama reactions, dipolar cy-
cloadditions, Claisen rearrangement, pinacol couplings,
conjugated additions, hydroformylation, and many others.
The rate enhancement may be due to a “hydrophobic ef-
fect” (i.e., the two organic reactants being closer together
because they are not very soluble in water). As an example,
the addition of phenylazide to norbornene (8.27) goes at the
relative rate of 5 in hexane, 7 in methanol, 72 in 94:6 water
tertbutyl alcohol, and 250 in 99:1 water N-cyclo-
hexylpyrrolidone.220
216 Chapter 8

8.27

8.28

In one case, a different product is obtained in a conden- cesses eliminate the need to protect and deprotect func-
sation (8.28).221 No dehydration of the product occurs. tional groups. A nitrogen atmosphere is unnecessary.227
Organic compounds that are insoluble in water can be (The use of indium(III) chloride228 and other Lewis acids
handled sometimes in micelles (microscopically fine as catalysts in water is discussed in Chap. 6.)
droplets) with or without the aid of ultrasound or surfac- Many of the reactions are catalyzed by transition metal
tants.222 catalysts. A variety of water-soluble ligands have been de-
Some organometallic reactions can be carried out in wa- vised to make the catalysts soluble in water. The most com-
ter.223 The Heck reaction, mentioned earlier, involves an mon is a sulfonated phosphine made by the sulfonation of
organopalladium intermediate. The ring opening metathe- triphenylphosphine (8.30) with fuming sulfuric acid.229
sis polymerization of norbornenes containing polar groups, A variety of other water-soluble ligands (8.31–8.33)
such as ethers and esters, can be done in water using ruthe- have also been used.
nium salt catalysts. In water, the ruthenium must coordi-
nate better with the olefin than the ether or ester. Aqueous
Barbier–Grignard-type reactions can be carried out with in-
dium, tin, and zinc metals in water.224 (Tin(II) chloride has
also been used.225) A typical reaction of this type is shown
in 8.29.226
When zinc is used in such reactions, ultrasound is often
used to keep the surface clean and thus promote the reac-
tion. Indium is nontoxic and resistant to oxidation by air. It
can be recovered electrolytically and recycled. Such pro- 8.30

8.29
Working Without Organic Solvents
8.31
8.32
8.32a
The reaction of phosphine-containing alcohols with 2-
sulfobenzoic acid cyclic anhydride (see 8.31) has been
used as a milder method of producing a water-soluble
phosphine than the use of fuming sulfuric acid.230 The
second phosphine (see 8.32) was made by the addition of
lithium diphenylphosphide to the commercially available
acrylamidesulfonate, then converted to the lithium salt.231
(Many other phosphine sulfonates have also been made
for this use.232) The guanidinium salts (8.32a) used in
aqueous Heck reactions are more stable to oxidation by
air than the sulfonated phosphines.233 Poly(acrylic acid)
salts can be modified (see 8.33) to incorporate phosphine
ligands.234 The one shown was used with rhodium in the
hydrogenation of 2-acetamidocinnamic acid to produce
the saturated acid in higher than 97% yield and 56% ee.
(The literature reports up to 93% ee under other condi-
tions; other phosphines containing–COONa groups have
also been used.235) Derivatives from polyethylene oxide
and polypropylene oxide have also been used as water-
soluble ligands.236 The ones shown in (8.4) were used
with rhodium in the hydroformylation of 1-hexene, 1-
octene, and 1-dodecene:
(C6 H5)3mP[C6 H 4-p-(OCH2CH2)nOH]m
(8.4)
m 1, 2, or 3
217
8.33
The yield of aldehydes at 95–97% conversion was was
90–91%. The catalyst goes into the organic phase at higher
temperatures and returns to the aqueous phase on cooling.
On the fifth cycle with 1-hexene, the conversion dropped
to 92% and the yield of aldehyde to 87%. A phosphine
containing a trimethylammonium group has been used
with ruthenium in a living ring-opening methathesis
polymerization.237
These water-soluble catalysts are especially useful
when the product is a separate organic phase that can be
separated continuously.238 Examples include the hydro-
formylation of propylene and the telomerization of dienes.
The catalyst in the aqueous phase can be used over and
over without loss. This includes reactions during which
the aqueous solution of the catalyst is supported on silica
or other support.239 A rhodium catalyst in water on silica
was 20 times more active in the hydroformylation of
methyl acrylate than the homogeneous counterpart.240 The
hydroformylation of methyl 10-undecenoate gave a 94%
yield of the corresponding 11-formyl compound.241 For
larger molecules, it was necessary to include a phase-
transfer catalyst such as dodecyltrimethylammonium bro-
mide. This lowered the normal/iso ratio below the 97:3 in
the foregoing example. Similar quaternary ammonium
phase-transfer catalysts242 have been used in the conden-
sation of aldehydes with ketones243 and with aqueous
Heck reactions.244
218
8.34
Reactions can also be carried out in microemulsions.
(Microemulsions have finer droplets of the oil phase than
the usual emulsions.) They have been used in the hydroxy-
carbonylation of iodobenzene (8.34).245
When the surfactant was sodium dodecyl sulfate, some
butanol had to be present to achieve the microemulsion. A
typical run used 2 mmol aryl iodide, 0.5 g surfactant, 1 mL
butanol, 10 mL water, and 2 mmol base. The butanol was
unnecessary with nonionic surfactants, such as the one de-
rived from 1-dodecanol with 23 eq of ethylene oxide. The
advantages of such a system include the following: (a) No
organic solvent is needed. The substrate is the oil phase. (b)
The microemulsions form without the need for vigorous
agitation. (c) No excess base is needed, in contrast with
some reactions in which phase-transfer catalysis is used.
(d) The surfactants can be recovered and recycled. They are
inexpensive and biodegradable.
In one case, fine droplets were reacted in a column with-
out the need for a surfactant. Cyclooctene was introduced
through a sparger at the bottom of a column containing an
aqueous solution of the oxidant, potassium peroxymono-
sulfate. The oxidation took place as the droplets rose to the
surface. The reaction was nearly 99% selective.246 The or-
ganic phase could be pumped around the loop repeatedly to
increase conversion. The epoxide product was collected by
filtration as the organic layer was pumped around the loop.
Conversion was over 60% in 3 h.
Ultrasound and microwave energy can help some reac-
tions proceed without an organic solvent. (Further detail on
the use of these types of energy can be found in Chap. 15.)
Consider the reaction of the aldehydes in 8.35.247
8.35
Chapter 8
No solvent, not even water, was used in the reaction, but
ethyl ether was used in the workup. The base was potas-
sium carbonate or hydroxide. Pyrazoles can be formed
from long-chain -diketones and aqueous hydrazine (8.36)
with the assistance of ultrasound.248 If there was no ultra-
sound, the reaction required 4 h at reflux.
Hydrotropic agents, such as sodium xylenesulfonate in-
crease the solubility of organic compounds in water. Dow
sells a hydrotropic disulfonate diphenyl ether as Dowfax
2A1 (8.37).
Aqueous sodium xylenesulfonate has been used to ex-
tract fragrances, such as 2-phenylethanol, as a mild replace-
ment for the usual steam distillation.249 The alcohol was re-
covered by dilution with additional water. The hydrotrope
could be reused after concentration of the aqueous phase. A
mixture of ortho- and para-chlorobenzoic acids was sepa-
rated by dissolving the ortho-isomer in water containing
sodium 2-butoxyethyl sulfate.250 The o-chlorobenzoic acid
was recovered by diluting the extract with more water to
precipitate it. Base-catalyzed condensations (8.38) have
been carried out with the aid of sodium 2-butoxyethylsul-
fate or sodium p-toluenesulfonate as hydrotropes.251
The reagents stayed in the aqueous phase. The product
precipitated as formed. The hydrotropic solution showed
no problems after being recycled four times. This method
has also been used in the Hantzsch condensation (8.39)
where, again, the product was recovered by filtration.
Cyclodextrins can also be used to make some organic
compounds that are insoluble in water go into aqueous so-
lution. These were discussed in Chap. 5.
A relatively low solubility in water may be enough for
Working Without Organic Solvents 219

8.36

8.37

8.38

8.39
220 Chapter 8

8.40

the desired reaction to take place. Chapter 4 included an ex-
ample where a suspension of powdered 2-naphthol in wa-
ter was oxidized by air in the presence of an iron(III) chlo-
ride catalyst to produce the corresponding binaphthol in
95% yield.252 The by-product quinones usually found
when the reaction is carried out in solution with stoichio-
metric amounts of metal-containing oxidants were absent.
Polyethylene glycol has been used as an analogue of wa-
ter in some cases. Ethers have been made (8.40) in 68–91%
yields using powdered potassium hydroxide (containing
12% water) in polyethylene glycol.253
Although organic solvents were used in the workup, it
might be possible to use filtration plus ultrafiltration, fol-
lowed by distillation instead. Hydroformylation of 1-hex-
ene has been achieved in polyethylene glycol by using a
cobalt catalyst containing polyethyleneoxy substitu-
tents.254 The catalyst phase was separated for reuse.
Polymerization in aqueous emulsions is common indus-
trial practice. The emulsion has a much lower viscosity
than a comparable solution in a solvent. It is possible to ob-
tain higher molecular weights in the emulsion because
there is no solvent present to act as a chain-transfer agent.
Frequently, the product emulsions can be used as such
(e.g., as adhesives or coatings).
molecules containing a hydrophobic unit and a hydrophilic
unit. The soap, sodium stearate, is an example. The polar
group can also be cationic, as in quaternary ammonium
salts, or nonionic, as in polyethyleneoxy units. Destructible
surfactants contain cleavable units so that after cleavage
the parts no longer act as surface-active agents. The most
common ones contain an acetal or ketal linkage that can be
cleaved by acid.256 Two typical ones are shown in 8.42
where R is a long hydrocarbon chain).
The problem has been to obtain ones that cleave rela-
tively quickly under mild conditions. Union Carbide is now
marketing a proprietary one made from glycerol for use in
treating wastewater. For example, the grease and oil left be-
hind when industrial rags and clothing are cleaned can be
separated by cleaving the surfactant with acid, which
breaks the emulsion.257 The two layers are then treated sep-
arately for recycle or disposal. The company suggests other
uses in paper and textile processing, metal working fluids,

VI. SURFACTANTS AND CLEANING

Surfactants are often used when reactions are carried out in

water. However, their presence in the final product may be
undesirable. In polymerizations, it is possible to use a poly-
merizable surfactant that becomes part of the final copoly-
mer.255 A typical one (8.41) contains an acrylate group.
Surfactants (i.e., surface-active agents) consist of 8.42

8.41
Working Without Organic Solvents
8.43
8.44
and other commercial uses. This technique may also be of
value in working up organic reactions run in water. Ideally,
there should be some way to recover the surfactant for re-
cycle to the next run. Collecting the parts and making the
acetal separately is a possibility.
Photodestructible surfactants have also been made.258
When the first one (8.43) is irradiated with light in the pres-
ence of base, phosphoric acid is eliminated. In the second
(8.44), nitrogen and sulfuric acid are lost.
A latex paint is an aqueous emulsion. After the paint
dries, the surfactant is still present and may interfere with
the resistance of the paint to washing to remove finger-
prints or other marks. A destructible surfactant would be
valuable in this application. It would have to destruct by the
action of light or air. Latex paints are not entirely free of
solvent. A few percent of a higher-boiling solvent, a coa-
lescing agent, is usually, but not always, necessary to form
a pinhole-free film from the particles of polymer after the
water evaporates. A typical one (8.45) is derived from
isobutyraldehyde.
Another approach is to try to develop more effective
surfactants that can be used at lower levels. A combination
of N-tetradecyldiethanolamine and copper(II) is effective
at 16% of the usual amount of surfactant in forming a mi-
croemulsion.259 The use of copper(II) is questionable for
8.45
221
many applications after which the metal ion might end up
in wastewater.
Soaps and detergents are surfactants used in cleaning.260
Soaps are salts of fatty acids (e.g., sodium stearate). Deter-
gents are salts of sulfonic acids, quaternary ammonium
salts, tertiary amine oxides, ethylene oxide adducts of alco-
hols, and phenols.261 Their use in cleaning to replace chlo-
rinated solvents262 was covered in Chap. 3, Sec. VII. (See
also the use of hydrogen peroxide,263 ethyl lactate,264 and
ultrasound265 to clean process equipment.) Some other en-
vironmental aspects of their use will be covered here
briefly.
Home laundry systems in Europe use 4 gal of water per
wash compared with 18–23 gal in the United States.266 The
trend toward lower temperatures in washing has increased
the use of enzymes in solid detergents.267 Because much of
the cost of doing the wash is in heating the water, the Eu-
ropean system appears to be better.
The sodium alkylbenzenesulfonates are an important
class of detergents. The original ones made by alkylating
benzene with propylene tetramer did not biodegrade, re-
sulting in foaming rivers, and such.268 The current linear
alkylbenzenesulfonates (8.46) made from -olefins are
biodegradable.
The second problem with detergents has been the use of
sodium tripolyphosphate (8.47) as a builder (i.e., an agent
to sequester the calcium and magnesium ions in the water).
This has caused eutrophication (excessive growth of algae)
of lakes and rivers receiving waste water.269
Fish kills have also resulted from wastewater. Various
replacements for phosphate are used in those places that
have banned phosphate. The use of zeolites is common.
Gluconic acid, prepared by the palladium-catalyzed air ox-
idation of glucose, can be used.270 Poly(acrylic acid) can be
used, but is not biodegradable.271 Poly(aspartic acid) (8.48)
made from maleic anhydride and ammonia solves this
problem.272
A product made from renewable raw materials has also
been active in this application. Oxidation of the amy-
lopectin fraction of starch with periodic acid cleaves some
vicinal diol structures to dialdehydes which can be oxi-
dized further to dicarboxylic acids.273 For good activity
222
8.46
8.47
over 80% of the original glucopyranose units must remain.
A 1:1 blend of a tertiary amine-N-oxide and an alcohol
ethoxylate cleaned hard surfaces without the need for phos-
phate.274 These detergents may not form complexes with
calcium and magnesium ions. Thus, the use of nonionic de-
tergents may obviate the need for a builder.
The alternative to not using a phosphate is to take it out
of the wastewater at the treatment plant.275 The recovered
phosphate can be used as fertilizer. This method is used in
Germany and Sweden.
Many surfactants are made from petroleum with haz-
ardous reagents. Sulfur trioxide was used with the carcino-
gen benzene to make the alkylbenzenesulfonates described
earlier. The carcinogen ethylene oxide is used to make
many nonionic surfactants from phenols and long-chain al-
cohols. A common surfactant, sodium dodecyl sulfate, is
made from an alcohol derived from coconut oil by reduc-
tion followed by treatment with sulfur trioxide. Long-chain
tertiary amines derived from natural fats and oils are quat-
ernized with methyl chloride. Perhaps this can be done with
8.48
Chapter 8
dimethyl carbonate. Soaps are made by hydrolysis of fats
and oils with sodium or potassium hydroxide. They are
biodegradable. The challenge is to obtain detergent activity
from compounds made from renewable sources so that
biodegradability will not be a problem.276
Henkel makes alkyl polyglycoside surfactants from al-
cohols derived from coconut and palm oils, and glucose de-
rived from cornstarch.277 The preparation can be done with
-D-glucosidase.278 Sucrose monoesters of long-chain
fatty acids can also be made enzymatically.279 A variety of
biosurfactants are produced by various organisms that can
be grown in culture.280
Thin films of titanium dioxide prepared by the sol–gel
technique from titanium alkoxides catalyze the photooxi-
dation of thin films of organic matter281 (as mentioned in
Chap. 3). The films are transparent and abrasion-resistant.
They can photocatalyze the oxidation of about 1–5 m/day
of organic film. Consistent activity in the oxidation of
stearic acid and benzene was observed over 300 h, as long
as some water was present. This technique may be useful in
self-cleaning windows, windshields, and architectural sur-
faces. The coating makes the windshield more hydrophilic
so that it does not fog. Condensed water forms a film, rather
than beads. Molds as well as dirt could be removed in this
way. The photocatalytic activity is increased by inclusion
of a little fluoride or platinum in the coating.282 The coat-
ing of titanium dioxide is said to be a good adsorbent and
photocatalyst for the destruction of formaldehyde in “sick”
buildings.283 Another technique for self-cleaning outside
Working Without Organic Solvents
surfaces might be to apply a perfluorocarbon that dirt
would not strongly adhere to, so that it would be washed off
by the next rain. This is analogous to the treatments applied
now to upholstery and carpets to repel dirt. Titanium diox-
ide has also been used with light to deactivate a pressure-
sensitive adhesive so that materials held by it (e.g., a ban-
dage) can be removed easily.284
VII. COATINGS
Thin films of organic compounds are often applied from
solvents. These films include adhesives, coatings for mag-
netic tapes, inks, paints, and varnishes. Over 11% of all
products have some kind of coating. Worldwide sales of
coating-based products are over 5 trillion dollars.285 A
number of reviews of surface coatings and paints are avail-
able.286 Several other reviews cover ways to minimize the
use of solvents in these.287 Much of the discussion that fol-
lows is taken from these latter reviews.
Waterborne coatings288 can replace solvent-containing
ones in many uses. Typical water-based paints are emul-
sions of polymers, such poly(vinyl acetate-co-butyl acry-
late), most of them containing a small amount of a higher-
boiling solvent as a coalescing agent. Thus, they do emit
some volatile organic compounds, but far less than if the
usual solvent-based paint or varnish was used. Waterborne
paints that are free of volatile organic compounds are being
developed. They cause less sensitivity to asthmatics than
regular waterborne paints.289 Many water-based coatings
contain polymers with carboxylic acid or secondary or ter-
tiary amine groups which are solubilized with a volatile
base, such as ammonia, or an acid, such as lactic acid,
which are emitted and should be trapped as the film
dries.290 Monomers that can be used to make polymers of
this type include acrylic acid, methacrylic acid, maleic an-
hydride, 2-dimethylaminoethyl methacrylate, and others.
Condensation polymers, such as polyamides, based on di-
ethylenetriamine have amine groups that enable the poly-
mer to dissolve at low pH.
Many automobiles and appliances are coated with a wa-
terborne primer applied by electrodeposition in a process
called electrocoating. The metal car or appliance is one
electrode. Either anodic or cathodic electrodeposition can
be used. This is better than a spray system with solvent in
8.49
223
that small recesses and sharp edges can be coated evenly,
for they, too, are part of the electrode. Paint utilization is
over 95%, in contrast with a spray system for which much
overspray would be lost or would have to be recovered. Af-
ter the car is coated, it is dried and baked to remove the am-
monia or small carboxylic acid to produce a water-insensi-
tive coating. In addition, the system may contain reagents
that undergo further reaction to cross-link the coating. If
blocked isocyanates are included, the blocking agent that
comes off with the baking will have to be trapped. If the
isocyanate is present as a cyclic dimer, there will be no
blocking agent to be trapped. (See Chap. 2 for this chem-
istry.) If a copolymer of glycidyl methacrylate is used, it
can react with amine groups in the formulation during the
baking. There are some limitations to this method. The
baked coating is usually an insulator, making it impossible
to apply another coat by this method. However, there are a
few systems that produce a conductive first coat so that a
second coat can be applied by the same method. The vat
that the car passes through is large. It would not be conve-
nient to change colors very often if topcoats were applied
in this way. The color of the primer coat does not matter.
Waterborne polyurethane coatings for wood and floors
can be based on prepolymers made by reacting diiso-
cyanates with 2,2-bis(hydroxymethyl)propionic acid.291
These are usually two-component systems in which mixing
occurs at the time of use (e.g., using a dual spray nozzle). It
is desirable to pick a polyisocyanate that will react faster
with an alcohol group than with water. 2-Hydroxyethyl
acrylate can be incorporated in the prepolymer to help
cross-linking. Inclusion of isocyanate dimers (uretdiones)
will allow later cross-linking. Water-based epoxy resins
may use a dispersion of a liquid epoxide in water that is
cured by a polyamine, or an acrylic polymer containing
carboxylic acid groups.292 Waterborne fluorochemical
coatings are used for nonstick, dirt-resistant, and corrosion-
resistant coatings.293 One system (8.49) uses an ammo-
nium carboxylate in one chain and an oxazoline in another.
As the ammonia is lost from the film, the carboxylic acid
formed reacts with the oxazoline to form an amide.
The clear, colorless coating resists graffiti, marine-foul-
ing organisms, solvents, acids, bases, and sodium chlo-
ride. It can also be used as a mold-release and ice-release
coating.
224
Electropolymerization of monomers can produce pin-
hole-free coatings on steel at room temperature and atmo-
spheric pressure in aqueous systems.294 The coatings tend
to be even because thin spots conduct electricity better and
cause more polymerization. An alternating copolymer pre-
pared in this way from styrene and the maleimide of 4-
aminobenzoic acid had a weight average molecular weight
of 146,000 and a glass transition temperature of 231°C. It
was stable to 350°C. under oxygen and showed good adhe-
sion to steel.
Powder coatings use neither solvent nor water.295 They
can give nearly zero emissions. Thick coats can be applied
in contrast with the more than one thin coats needed with
solvent-borne coatings. Overspray can be reused so that
there is no waste, in contrast with the lost overspray with
some sprayed coatings. A thermoplastic polymer can be
used for the powder. Alternatively, cross-linking can be
done after the powder is on the object being coated. One
method is to dip the hot object in a fluidized bed of the pow-
der. Another is to spray electrically charged powder on to
the object, which is given the opposite charge. The object is
then heated to melt the powder. The powder must not melt
or sinter or react under normal shipping or storage condi-
tions. Typically, the glass transition temperature of the pow-
der is 50–55°C. Then, it is expected to cure to a film free of
pinholes at the lowest possible temperature. It has been a
challenge to lower the curing temperatures so that the tech-
nique can be used on plastics as well as with metals. A way
around this is to melt the powder at a modest temperature
and then to cure it with light or an electron beam.296 One
method uses a methacrylate prepolymer containing bisphe-
nol A dimethacrylate as a crystalline cross-linking agent, so
that the viscosity of the initial melt is low.297 (Morton (now
Rohm & Haas) and Ferro both sell proprietary powder coat-
ings for use on wood.298) Another method is to apply the
powder coating to the mold, then to mold the plastic into it.
Flame spraying, in which the polymer is melted by brief
contact with a flame and hits the object to be coated as
molten droplets that form a pinhole-free film is another pos-
8.50
Chapter 8
sibility.299 Traffic stripes on roads may be made of thermo-
plastic polymers applied in this way. Laser ablation of flu-
oropolymer films has been used to apply coatings of
poly(tetrafluoroethylene).300 The polymer depolymerizes
and repolymerizes in the process. Powder coatings can be
glossy, or flat (nonglossy), if a flatting agent has been
added.
The process consumes less energy than a system using
solvent spraying. A lot of air has to be passed through to
prevent fires and explosions in the latter case, and all of it
has to be heated, at least in winter. However, powder sys-
tems must be handled in a way that prevents dust explo-
sions. The use of an inert gas, such as nitrogen, to prevent
this is a possibility. Application of the powder as an aque-
ous dispersion is sometimes used to prevent it. This also al-
lows polymers with lower glass transition temperatures and
possibly lower-baking temperatures to be used. The water
has to be evaporated before the final film coalesces and
cures. Another limitation is the work required to clean the
equipment between color changes. If one apparatus can be
dedicated to one color, then this is not a problem. It has also
proved difficult to incorporate metal flake pigments into
powder coatings.
A popular type of powder coating consists of a carboxy-
terminated polyester mixed with a diepoxide.301 The epox-
ides include bisphenol A diepoxides, triglycidylisocyanu-
rate–and epoxidized vegetable oils. Blocked isocyanates
are also used in powder coatings.302 The use of oximes of
hindered ketones, such as diisopropyl ketone, allows de-
blocking at lower temperatures than with ordinary oximes,
such as that from 2-butanone. This system cures at
129–140°C. Many current systems cure at 165–200°C. Re-
moval of all of the diisopropylketone oxime out of the coat-
ing during curing could be a problem. The ketone oxime or
other blocking agent would have to be trapped from the ex-
haust air for reuse. If the diisocyanate is present as a cyclic
dimer (uretdione) that opens on heating, there will be no
emissions to trap.303 Another system that evolves nothing
on curing uses ketimines, which react through their enam-
Working Without Organic Solvents
8.51
ine isomers with isocyanates (8.50) to form polyureas.304 It
may be suitable for powder coatings, or for a 100% solids
coating applied from a dual spray nozzle.
Powder coatings are used on furniture, lawn mowers,
appliances, auto fittings, trucks, store shelving, exercise
equipment, aluminum extrusions, and so forth. They are
useful on pipes when thick coatings are needed.305 Pipeline
joints can be coated in the field by this method. An alterna-
tive is to use a heat-shrinkable sleeve of polyethylene.
Coatings cured by light or by electron beam radiation306
use no solvents and produce virtually no emissions. The
cure can be fast (e.g., less than 1 s). Energy usage is less
than that with solvent or waterborne coatings. They do
have some limitations. Light does not go around corners.
Pigments can interfere with the passage of light. Systems
that cure by a free radical mechanism are inhibited by air.
This means that an inert atmosphere must be used. An al-
ternative is to use protective waxes that bloom to the sur-
face to keep oxygen out. It is difficult to incorporate stabi-
lizing antioxidants in systems that cure by free radical
polymerization. The high viscosity of the prepolymer is
lowered by dilution with a polymerizable monomer. If this
monomer is an acrylate, skin irritation and sensitization are
possible. Sometimes, methacrylates are used to avoid this.
It is desirable to cure all of the monomer so that it will not
leach out later. Shrinkage that interferes with adhesion is a
problem with the polymerization of vinyl monomers. Thus,
enough acrylate groups must be present for a fast cure, but
not so many that shrinkage is excessive.
Polyester acrylates and urethane acrylates are in com-
mon use.307 Cationic systems use vinyl ethers, such as tri-
ethyleneglycol divinyl ether, epoxides, and polyols. These
225
avoid some of the problems of the acrylates. Skin irritation
is much less of a problem. Shrinkage is less with ring-open-
ing epoxides. Cures are not inhibited by oxygen, but they
are slower and may require heat for completion. The pres-
ence of pigment is less of a problem. The photoinitiators308
used, such as a triarylsulfonium tetrafluoroborate, leave
traces of acid in the coating. The photoinitiators for curing
the acrylates tend to be benzophenones and benzoin deriva-
tives. Work is being done to find photoinitiators that work
with visible light, which is absorbed less by pigments.309
Two such initiators are shown in 8.51.
Some cures can even be done in sunlight in 2 min using
the acylphosphine initiator (8.52).310
Inhibition of the polymerization by air was controlled
by use of 1:1 diacrylate–poly(methyl methacrylate) mix-
tures or by using the acrylate in a laminate between two
glass plates. These cost-effective cures use no external en-
ergy and no lamps. Composites of glass fiber and epoxides
from vegetable oils have been cured in sunlight with di-
aryliodinium and triaryl sulfonium salts in 25 min.311 Fur-
ther work is needed to speed up this photocationic cure.
8.52
226
No photoinitiator is needed when the acrylates are cured
by electron beams. The need to use a reactive monomer
diluent to lower the viscosity is lessened by the use of hy-
perbranched or dendritic polyester methacrylates.312 In one
case, 15% of trimethylolpropane triacrylate was used as a
cross-linking monomer. Compact molecules have lower
viscosities than linear ones. Dendrimers are spherical
molecules made by repeated branching from a multifunc-
tional core.313 In this case the hydroxyl groups on the sur-
face have been converted to methacrylates. In addition to
the low viscosity, these materials have higher curing rates.
If water-based, radiation-curable latexes314 are used, there
is no need to use a reactive monomer to lower viscosity.
However, more energy and time are needed to remove the
water before turning on the light.
Radiation-cured coatings are used most on flat surfaces.
They work well on vinyl flooring and in coil coating. The
latter involves coating sheet metal that is fabricated into a
variety of shapes and structures after coating. Radiation
curing is suitable for heat-sensitive materials such as paper,
wood, and some plastics. It is common with printing inks,
for which a fast cure is important. In Europe, furniture parts
are coated before assembly of the furniture. In the United
States, where the furniture is assembled first, solvent-based
nitrocellulose lacquers are preferred as coatings. It should
be possible to coat furniture after assembly with a system
with enough lamps and mirrors so that all parts of the fur-
niture receive adequate light. Photocationic initiation has
the best chance of working. It should also be possible for
the United States to switch to the European system. An-
other option would be to switch to more furniture molded
of plastic. Cross-linked scratch-resistant coatings are ap-
plied to eyeglasses, to plastic headlights for cars, and to
windows by radiation curing. Optical fibers for communi-
cation are also coated by radiation curing.
There are some other ways to apply coatings without the
use of solvents. Plastisols315 involve the use of a paste of
polyvinyl chloride particles in a plasticizer. Metal objects
dipped in this can then be heated to harden the coating by
dissolution of the plasticizer into the polymer. An example
would be a wire rack for a dishwasher. Colored paint films
can be laminated to plastics such as automobile parts and
siding for houses by molding.316 Ideally, the dry paint film
would be prepared by extrusion or other means that
avoided the use of solvent. It is also possible to produce a
coating from two monomer ingredients that polymerize in
8.53
Chapter 8
flight. Polyurea coatings317 can be made in this way using
a dual spray nozzle. Enough polymerization must occur in
flight so that the coating will not sag, but not enough that
leveling does not occur. It should be possible to extend this
to single monomers or prepolymers that can be polymer-
ized by cationic initiation by adding the catalyst at the
spray nozzle. Ultrasonic spray nozzles might give the best
results. The simplest systems to try would involve flat, hor-
izontal surfaces, such as coil coating or flooring.
Silicon dioxide films can be applied to plastics by
plasma or glow discharge polymerization of silanes, such
as tetramethoxysilane and hexamethyldisiloxane.318 These
films can serve as oxygen barriers on polypropylene film to
replace poly(vinylidene chloride) coatings. Aromatic ether
amides have also been made that afford good oxygen bar-
riers to replace poly(vinylidene chloride).319 The sol–gel
process has been used to apply hard scratch-resistant coat-
ings to plastics.320 Coatings of silicon dioxide are also oxy-
gen barriers for films of polypropylene and poly(ethylene
terephthalate). Application of such coatings to the insides
of poly(ethylene terephthalate) soda bottles might allow
them to be used as refillable containers, thus reducing plas-
tics consumption and waste.
High scratch resistance on plastics has been obtained by
the reaction 8.53. (This process does give off a lower alco-
hol which will have to be recovered for recycle.)
A possible alternative is to graft polymerize a vinyltri-
alkoxysilane to the surface of the polymer for later cross-
linking by moisture.321 It may be possible to prepare dia-
mond coatings that are good scratch-resistant oxygen
barriers using the three-laser technique.322 In contrast with
earlier methods, it uses carbon dioxide at room temperature
without a vacuum. It has been used primarily on metals.
This could also make plastic dinnerware more acceptable
in the home. The dinnerware would be light in weight, un-
breakable, and free of scratches and stains.
A pulsed plasma has been used to prepare pinhole-free
films from relatively nontoxic N-vinylpyrrolidone.323 The
pulsing reduced fragmentation of the monomer and cross-
linking. This method should be tried with other monomers.
Plasmas are often used for the modification of polymer sur-
faces.324 These methods are relatively rapid and use no sol-
vent. Decorative coatings of TiN and other inorganic com-
pounds can be applied to metals and other inorganic
substrates by sputtering, chemical vapor deposition, plas-
mas, and such, as described in Chap. 4.325
Working Without Organic Solvents
8.54
Coatings can fail from poor surface preparation, pin-
holes, lack of resistance to light, or other causes.326 Some
coatings have been designed to assimilate oil and to dis-
place water from surfaces so that surface preparation can be
skipped or minimized.327 One such polymer is 8.54. These
systems need further development before they can come
into common use.
Car painting328 is the largest source of solvent emissions
in Delaware. It should be possible to finish a car using the
methods outlined in the foregoing, especially as some of
them are already used on trucks and lawn mowers. A typi-
cal finish for an automobile includes a zinc phosphate pre-
treatment for corrosion resistance, a primer put on by elec-
trocoating, a second coating put on by powder coating, a
waterborne colored basecoat, and finally a solvent-borne
clear coat to protect the finish from acid rain, bird drop-
pings, and such.329 General Motors Buick uses a two-com-
ponent polyurethane clear coat. Glamour finishes, such as
those containing metal flakes, are popular. Luster pigments,
based on very thin layers of metal oxides on mica (where the
color comes from interference patterns), can be used in
powder coatings to obtain the same effect.330 These pig-
ments are transparent to ultraviolet light so that radiation
curing can be used. Occasionally, the clear topcoat has been
waterborne.331 A consortium of United States automakers
opened a facility in Michigan to test powder coating clear
coats in August 1996.332 A clear coat from PPG that con-
tains a patented flow additive has been used on 50,000
BMW cars, saving up to 1.5 kg of solvent per vehicle.333 Be-
cause trucks and lawn mowers can be finished by powder
coating, part of the problem may be the public preference
for glamour finishes. The chromium-plated bumper disap-
peared for economic reasons. It is possible that adding a 500
dollar surcharge for a car with a glamour finish might reduce
the solvent emissions in Delaware. A new system that uses
a plasma to clean the steel and put on an alkyl silane finish
can replace the zinc phosphate steps, providing superior
corrosion performance, eliminating wastewater and making
it easier to recycle the car at the end of its useful life.334
In contrast to the localized emissions of auto assembly
plants, printing335 with solvents is done in many small scat-
227
tered plants. Eighty percent of printing plants have fewer
than 20 employees. The U. S. Environmental Protection
Agency (EPA) has set up a joint project to help them re-
duce emissions.336 Even with solvent recovery and other
emission control devices, publication gravure printing
alone emits 26 million lb/year of toluene.337 A waterborne
ink for this use has been demonstrated in Europe. A good
plant can capture up to 96% of the solvent from printing,
but 80% to the low 90%s is more common.338 Waterborne
and radiation-cured inks are in the forefront of the effort to
reduce these emissions.339 The waterborne inks still con-
tain small amounts of solvent. Overprint coatings contain
1–5% solvent, down from 10–12% 5 years earlier.340 A
typical water-based ink contains a polymeric carboxylic
acid that is neutralized with ammonia or an amine.341
These inks work well with porous materials, such as paper
and cardboard, but are harder to use with plastics, which do
not absorb moisture. An ink containing no solvent is used
for the commercial printing of checks by Deluxe Corpora-
tion.342 The plant has zero volatile emissions. The presence
of carboxylic acid groups in the resin allows clean-up of
equipment with aqueous base. Radiation-cured inks are
finding increased use in spite of the fact that they cost three
times as much as regular inks.
Although ballpoint pens are said to “write dry” on
porous materials such as paper, the ink in them still con-
tains some solvent.343 A typical ink may contain 30%
phenylglycol and 8% 1,2-propanediol.
There are about 40,000 screen printers in the United
States, each with an average of 14 employees.344 The
screen is a stencil that must be cleaned with solvent be-
tween runs. Solvent recovery on-site by distillation is re-
ducing the amount of new solvent needed. Less hazardous
solvents are now being used (e.g., a mixture of propylene
glycol monomethyl ether, propylene glycol monomethyl
ether acetate, and cyclohexanone). High-pressure jets of
aqueous emulsion cleaners are also being used. The next
step in the evolution of the industry is to switch to nonim-
pact printing using ink jets, which will eliminate the
screens.
Hot-melt345 and waterborne adhesives and sealants are
replacing those with solvent.346 The most common hot melt
adhesives are based on copolymers of ethylene and vinyl
acetate. They bond by solidifying on cooling, which can be
fast if the substrates are at room temperature, as in book-
binding or carton-sealing. Efforts are being made to find
ones that will be easier to handle in the repulping of paper
bonded with them. (Putting carboxylic acid groups into the
hot-melt adhesive should help.) The iron-on patch for
mending clothing is a hot melt adhesive based on a
polyamide. A hot-melt adhesive made from an isocyanate-
terminated polyurethane is cured by moisture.347 The most
228
8.55
common aqueous emulsion adhesive is based on poly(vinyl
acetate-co-vinyl alcohol). It is made by the emulsion poly-
merization of vinyl acetate followed by partial hydrolysis.
Goodyear is using a water-based adhesive in all of its tire
retreading centers.348 Waterborne and hot-melt adhesives
are preferred over solvent-based ones for cars, except
where mechanical fasteners are needed for part removal.349
It is also possible to bond without an adhesive. Two
pieces of plastic or two pieces of metal can be bonded by
ultrasonic welding. Many plastic films are joined by heat
sealing (i.e., heating with a hot metal bar until the films join
together). Bags for food items are often made this way.
Mixtures of fibers, in which one is a lower-melting ther-
moplastic fiber, can be bonded by melting the lower-melt-
ing fiber while pressing against the other one. This is done
sometimes with a pattern on a hot roll to make nonwoven
fabrics. A variant is to spin a bicomponent fiber in which
one component is lower melting. A high-powered diode
laser has been used to bond polypropylene without any en-
vironmentally unfriendly pretreatments.350
Isocyanate-based sealants are in common use. The toxi-
city of the isocyanates has led to a search for less toxic al-
ternatives. One is based on the reaction of bis(acetoac-
etates) with diamines (8.55).351 The sealant cures when the
bis(enamine) is mixed with more of the starting bis(ace-
toacetate) in the presence of a catalyst.
Magnetic tapes are usually coated with coatings from
solvents, such as methyl ethyl ketone, methyl isobutyl ke-
tone, and toluene. Aqueous replacements can eliminate all
or nearly all of the solvents.352 One system used iron oxide
in a blend of a polyurethane and ethylene–vinyl chloride
copolymer emulsions thickened with hydroxyethyl cellu-
lose, which was cross-linked with a melamine–formalde-
hyde resin. Coating was done at line speeds of 100 m/min.
The whole system proved to be 15% cheaper than coating
from solvent. In another system, traces of methanol are
evolved on drying and would have to be captured. This re-
places a line where 600 kg/h of solvent would have to be re-
covered and recycled.
Hair sprays are used by many persons to hold their hair
in place. A typical spray consists of a polymer in ethanol
and a little water with dimethyl ether and n-butane as pro-
pellants.353 These organic compounds contribute to ground
level ozone. They also are a fire hazard. Efforts are under-
Chapter 8
way to reduce these problems. Dilution with more water
gives an unacceptable spray. The use of different polymers
in high-solids formulations in ethanol containing more wa-
ter is being explored. Eastman Chemical has prepared a
water-dispersible sulfopolyester in a melt without solvent,
with no toxic by-products.354 This polymer can be used in
55% ethanol. The need for a propellant can be eliminated
by using a finger or rubber bulb-actuated pump. If hair
styles change so that ponytails and braids become popular
again, the severity of the problem will decrease.
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RECOMMENDED READING
1. TH Grindstaff. Chem Eng News Nov 7 1994:3 [syntheses
without solvents].
2. F Toda. Acc Chem Res 1995; 28:480 [solid-state organic
chemistry].
3. A Lubineau. Chem Ind 1996:123 [reactions in water].
4. Alternative metal finishes. EPA/625/R-94/007, Sept 1994.
Working Without Organic Solvents
5. Organic coatings replacements. EPA/625/R-94/006, Sept
1994.
6. ZW Wicks Jr, FN Jones, SP Pappas. Organic Coatings: Sci-
ence and Technology, vol 2. Wiley, New York, 1994:
226–228, 249–251, 268–271.
7. JM Tanko, JF Blackert. In: PT Anastas, CA Farris, eds. Be-
nign by Design: Alternative Synthetic Design. Am Chem Soc
Symp 577, Washington, DC, 1994:98. [reactions in sc CO2]
EXERCISES
1. Visit a laboratory or plant with an extruder.
2. Pick an organic reaction that is normally run in a
solvent and tell how you might run it in an extruder.
If possible, pick one that is used industrially.
3. Visit a local dry cleaner, metal parts fabricator,
239
print shop, or paint shop to see how successful they
have been in eliminating solvent emissions.
4. Check the Toxics Release Inventory, or a compara-
ble compilation, to see what point sources of sol-
vents are near where you live. Try to figure out al-
ternative processes that will significantly reduce or
eliminate these emissions.
5. If possible, visit a plant that uses powder coatings or
radiation-cured coatings.
6. If there is a supercritical carbon dioxide chromato-
graph in an analytical laboratory near you, see how
the material is handled.
7. Poll your friends to see how many of them prefer
shiny cars, shoes, floors, and furniture. In many
cases, substituting a plain finish for the glamour fin-
ish would reduce solvent use. It has been possible to
eliminate the shiny metal bumpers and strips on
cars.
9
Biocatalysis and Biodiversity
I. BIOCATALYSIS
A. Advantages and Limitations
Chemical reactions are usually carried out under rigorous
conditions. They often involve highly reactive ingredients,
which may be toxic or carcinogenic, that are used in or-
ganic solvents. High temperatures and pressures may be in-
volved, especially in the production of commodity chemi-
cals. Biocatalysis offers the possibility of making many of
the products that we need in water at or near room temper-
ature. It uses whole organisms, usually microorganisms, or
the enzymes from them, to carry out the chemical transfor-
mations.1 It is an aspect of biotechnology. Chemoenzy-
matic syntheses, i.e., those sequences of reactions where
both chemical and biological steps are involved, are be-
coming increasingly common.
Biocatalysis offer many advantages:a
1. Often run in water with no need for organic
solvents
2. Often run at or near room temperature at atmo-
spheric pressure
3. No toxic metal ions
4. No carcinogens
5. No noxious emissions, just carbon dioxide
6. No toxic wastes: wastes can be used as animal
feed or composted.
7. Often use organic wastes as starting materials.
8. Higher selectivities: it is often possible to react
only one of two similar sites.3
9. Chiral compounds can be produced.
241
10. No protecting groups are needed in reactions.
11. Less energy is needed.
About 7% of petroleum is used to make chemicals. Bio-
catalysis offers a method to switch to a base of renewable
materials for a sustainable future. By so doing, it will help
moderate global warming; its inherently cleaner chemistry
will reduce air and water pollution.
There are limitations to biocatalysis that current re-
search is endeavoring to overcome:
1. The reaction may be slow, especially if done in an
organic medium.
2. The run may have to be quite dilute.
3. The enzyme may be expensive and difficult to re-
cover for reuse.
4. The enzyme may lose activity too quickly, espe-
cially if used at elevated temperatures.
5. The recovery of the product from dilute solution
may be complicated and expensive.
6. The product may inhibit its further formation.
7. It may be difficult to obtain a pure enzyme, free of
contamination by other enzymes that might de-
grade the substrate or produce by-products.
8. It may be difficult to shift the equilibrium in the re-
action so that 100% conversion to the desired
product takes place.
9. Conditions for optimal growth of the organisms
may be difficult to work out.
10. Production of the desired product may require the
addition of an elicitor or altered growing
conditions.
11. The organism may not secrete the product into the
medium so that the cells have to be destroyed to
recover the product.
242
B. Industrial Products Produced by Biocatalysis
Hinman4 lists the major products produced from fermenta-
tion today as follows:
Product Metric tons/yr
Ethanol 15 million
Monosodium glutamate 1 million
Citric acid 400,000
Lysine 115,000
Gluconic acid 50,000
Penicillin5 15,000
These are usually made from glucose, starch, molasses, or
other such compounds, with added nutrients from corn
steep liquor, soybean meal, blood meal, and so on. In addi-
tion, there are many valuable compounds made in lower
volume.6 These include lactic acid, malic acid, L-phenyl-
alanine, L-aspartic acid, other amino acids,7 flavors and fra-
grances,8 steroids, vitamins, other antibiotics, xanthan
gum, tissue plasminogen activator, human growth hor-
mone, erythropoietin, and many enzymes.9 L-Aspartate is
made from fumarate using an aspartase from Escherichia
coli; L-phenylalanine by addition of ammonia to trans-cin-
namic acid using phenylalanine ammonia lyase from
Rhodotorula rubra; and L-malate (9.1a) by the hydration of
fumarate using a fumarase from Brevibacterium flavum. It
can also be produced in up to 109 g/L by a strain of Sac-
charomyces cerevisiae.10 (Enzymes are usually named af-
ter the reaction that they catalyze with the suffix ase11.) The
first two products are converted to a dipeptide, aspartame,
which is a popular artificial sweetener (9.1).
A new plant for the production of riboflavin in Germany
9.1
9.1a
Chapter 9
will cut the cost of the current chemical syntheses in half.12
The worldwide market for enzymes13 is about 1 billion dol-
lar, each year.14 The major use is in laundry detergents
where they save energy by allowing washing to proceed at
lower temperatures.15 They are also used extensively in
food processing (e.g., production of high-fructose corn
syrup and the use of pectinases to clarify fruit juices). Over
60% of the enzymes are recombinant products.16
Fermentation has been used in the production of foods
and drinks since the days of antiquity. A recent applica-
tion is the large-scale production of yogurt. Before the ad-
vent of cheap petroleum, a variety of other commodity
chemicals were produced by fermentation. Acetone and n-
butyl alcohol were produced by Clostridium aceto-
butylicum.17 Ethanol, which was all made from fermenta-
tion, is now made in part by the hydration of ethylene.
Acetic acid is now made largely by the carbonylation of
methanol (9.2) using a rhodium catalyst in the presence of
iodide ion.18
Acetic acid produced by fermentation does not involve
toxic carbon monoxide or methanol, nor expensive
rhodium. Products from petroleum or natural gas are
cheaper because they do not include the cost of natural re-
source depletion or of global warming. (See Chap. 17 for a
discussion of such costs.) It is also possible that application
of some of the newer techniques will improve the fermen-
tations so that they give better yields and are more cost-
competitive. This is one of the keys to a sustainable fu-
ture.19 Industrial research in this area is increasing.20
9.2
Biocatalysis and Biodiversity
C. Techniques of Biocatalysis
A variety of techniques are being studied in an effort to re-
move the limitations of biocatalysis.21 Some of these will
now be examined together with some examples of their
use.
1. Production of Ethanol
The methods used to prepare ethanol will be examined
first, because it is the chemical produced in largest volume
by fermentation.22
The Saccharomyces cerevisiae often used to convert
sugars into alcohol is inhibited by too much substrate and
too much product. A typical final concentration of ethanol
is 5.9%. By immobilizing the cells and adding more glu-
cose and nutrients stepwise every few hours ethanol was
produced in up to 15.0% concentration.23 Another way to
improve the process is to hunt for more tolerant organisms.
A Saccharomyces used to make palm wine in Nigeria tol-
erated 50% sucrose solutions and led to a concentration of
21.5% ethanol.24 Tropical yeasts can also tolerate some-
what higher temperatures (e.g., 40°C), which leads to faster
rates. Thermophilic bacteria that can use both five-and six-
carbon sugars make ethanol ten times as fast as the usual
fermentation with yeast.25 Addition of zeolites to fermen-
tation of molasses with S. cerevisiae increased the rate
53%.26 This is thought to involve the removal of inhibitors,
such as toxic metal ions. Activated carbon and alumina
have also been used for this purpose.27 This allows the
same medium to be used over a longer time.
Continuous removal of the ethanol by extraction with n-
dodecanol has been used with an immobilized yeast in an
18-day run in an effort to lower the cost of production.28
The main by-product was glycerol, which also has impor-
tant uses as a humectant. The production of ethanol and its
conversion to biodiesel fuel was carried out in one step us-
ing a two-phase system of oleic acid and an aqueous phase
with S. cerevisiae plus a lipase from Rhizomucor miehei.29
Continuous filtration of the cells with hollow-fiber mem-
brane separation of the ethanol from the filtrate has also
been used.30 Ethanol was obtained from glucose in 90%
yield by a system run for 150–185 days with continuous
stripping of the ethanol by distillation.31 Continuous re-
moval of the ethanol by pervaporation through membranes
was discussed in Chap. 7. Other methods of continuous re-
moval include gas stripping, product removal by a solid
phase, and the use of two aqueous layers.32
Costs might be lowered by combining steps and by start-
ing with cheaper raw materials, such as wastes. Simultane-
ous saccharification and fermentation of cellulose (a poly-
mer of glucose) has been accomplished by combining a
243
cellulase and a -glucosidase.33 Cassava starch (another
polymer of glucose) has been converted to 10.5% ethanol
by a mixed culture of Endomycopsis fibuligera and Zy-
momonas mobilis.34 The first organism converted the
starch to sugar, which was then converted to ethanol by the
second. The addition of 0.01% glucoamylase allowed the
production of 13.2% ethanol in a yield of 98%. Cheaper
substrates include stillage from sugar beets,35 agricultural
wastes, waste paper, and others.36 To obtain favorable
yields, both the cellulose and the hemicelluloses (polymers
of five-carbon sugars) of lignocellulosic wastes must be
used.37 In addition, inhibitors, such as furfural, phenol,
acetic acid, aromatic compounds, and metal ions may have
to be removed from lignocellulosic hydrolysates. In one
case, acetic acid in hardwood spent sulfite liquor was re-
moved by a mutant S. cerevisiae that grows on acetic acid,
but not on xylose, glucose, mannose, or fructose.38 Can-
dida parapsilosis converted xylose to xylitol selectively in
the presence of glucose and mannose in a hydrolysate of as-
pen wood.39 A mixed culture of S. cerevisiae and C. she-
hatae produced both ethanol and xylitol simultaneously
from a mixture of glucose and xylose.40 Both products
were also obtained from the latter organism growing on xy-
lose alone.41 Xylitol has also been produced from xylose by
Debaryomyces hansenii.42 Xylitol has a high sweetening
power, does not cause dental caries, and is an insulin-inde-
pendent carbohydrate for insulin-dependent diabetics. Its
potential market is large, but not nearly as large as the po-
tential market for ethanol used as fuel.
Klebsiella oxytoca was engineered to include genes to
produce enzymes for the hydrolysis of both cellulose and
hemicellulose.43 It was able to produce ethanol in 83%
yield from mixed office waste paper. The yield was 539
L/metric ton of waste. The paper did have to be pretreated
with water (with or without 1% sulfuric acid) at 140°C for
30 min. The need for the cellulase was reduced by recy-
cling some of the residue to reduce costs. A plant is being
built in Louisiana to use this process on sugarcane
wastes.44 The use of intermittent ultrasound in such sys-
tems can cut the amount of enzyme needed in half.45 The
residue after converting corn to ethanol was a good ingre-
dient for food for Tilapia (a fish popular for aquaculture).46
Credit for such by-products helps reduce the overall cost.
The U. S. National Energy Laboratory has used a genet-
ically engineered Zymomonas mobilis to convert agricul-
tural residues and sawdust to ethanol in a process that uses
both the glucose and xylose. It is estimated that this will re-
duce the price of ethanol from $1.20/gal, to $0.70/gal.47
Recombinant E. coli converted willow wood to ethanol,
which is estimated to cost $0.48/L.48 The market price in
Sweden is $0.35/L. It is estimated that the price could be
reduced $0.063/L. if the process started with waste and an-
244
other $0.063/L if the ethanol was not distilled. This makes
a good case for starting with waste paper and using perva-
poration to isolate the ethanol, then another membrane to
dehydrate it. Critics contend that ethanol from corn is not a
renewable energy source because it takes at least a barrel of
petroleum to produce a barrel of ethanol.49 This includes
the energy needed to make and apply the fertilizer, tilling
and harvesting the corn, hydrolyzing the corn starch, dis-
tilling the ethanol, and so on. The use of wastes and the use
of membranes in the process will reduce the need for
petroleum. It is also possible to use biodiesel fuel (obtained
from vegetable oils by alcoholysis) as well as energy from
the wind, the sun, and hydropower in the processing. The
critics do not mention the costs of natural resource deple-
tion and global warming. To put the problem into perspec-
tive, enormous savings of fuel would result if Americans
lived in more compact cities and went from place to place
by means other than driving alone in their cars.
2. Immobilization of Enzymes50
Altus Biologics purifies and crystallizes enzymes, which
are then cross-linked with glutaraldehyde.51 This results in
marked improvements in stability to heat, extremes of pH,
exogeneous proteases, and organic solvents. Full activity
remained for a product from thermolysin after 4 days at
65°C. More than 95% of the activity remained after 1 h in
50% aqueous tetrahydrofuran at 40°C, compared with only
36% for free thermolysin. The enzymes can be used in re-
gioselective acylation of alcohols and amines, synthesis of
peptides, resolution of acids and alcohols, chemoselective
hydrolysis of esters and amides, modification of sugars,
and in making modified penicillins. They can be filtered off
and reused 10–20 times so that final productivities of
1:1000 to 1:100,000 catalyst per product can be obtained.
Rates of hydrolyses catalyzed by these enzymes in organic
solvents can equal or exceed those in water. Microporous
cross-linked protein crystals (“bioorganic zeolites”) have
also been used to separate molecules by size, chemical
structure, and chirality.52
Whole cells are often immobilized in calcium alginate
gel beads.53 Lactic acid bacteria immobilized in this way
have been used to recover the protein from cheese whey
(the liquid left over from the making of cheese).54 The lac-
tic acid that is formed precipitates the proteins. Encapsula-
tion in this way increased the stability of Bacillus sphaeri-
cus to heat and light for use in mosquito control.55 An
enzyme was immobilized on magnetite in this way.56 This
was used in a magnetic field that stabilized the fluidized
bed in the hydrolysis of maltodextrin. Calcium alginate
beads containing -glucosidase were treated with tetram-
ethoxysilane to encapsulate them with silica.57 This gave
Chapter 9
excellent protein retention and thermal stability, with an
operational life of several months.
Immobilized biocatalysts58 often have lower activity
owing to diffusion and access problems. An enzyme im-
mobilized on a macroporous monolith was more active
than one in beads, presumably because of better accessibil-
ity to the active sites.59 Enzymes have also been encapsu-
lated in porous thin-walled polymeric microcapsules.60
Biocatalytic plastics made by acryloylation of subtilisin
and -chymotrypsin followed by free–radical-catalyzed
polymerization with vinyl monomers, such as methyl
methacrylate, styrene, and vinyl acetate, in the presence of
a surfactant contain up to 50% enzyme.61 They are ten
times less active than the free enzyme in water, but much
more active in organic media than the free enzyme. There
is no loss in activity after storage for several months at
room temperature. This provides a way to put enzymes into
tubing, membranes, coatings, and such. The method has
been suggested for nonfouling paints for ships. Biocatalytic
plastics have also been made by incorporating enzymes in
polyurethane foams.62
There are some cases in which the immobilized enzyme
has a higher activity than its free form. A lipase put on sil-
ica by the sol–gel method, using an alkyltrimethoxysilane,
had twice the activity of the free enzyme.63 It retained 63%
of its activity after 3 months (i.e., much more than that of
the free enzyme). It was stable enough mechanically for
use in fluidized beds. Inclusion of Fe3O4 nanoparticles in
the preparation made the enzyme easy to separate. Some
enzymes trapped in silica by the sol–gel process are as ac-
tive as the free enzymes and are much more stable ther-
mally and to pH changes.64
An immobilized Candida cylindracea lipase retained
80% of its activity after 336 h of operation.65 It was 37
times as stable as the native enzyme. If glucose oxidase was
physisorbed on to silica, its activity dropped to one-sixth in
3 weeks.66 If it was attached covalently by a triethoxysilane
method, the activity increased over the 3-week period. At-
tachment at more than one point can enhance stability. A
thermophilic esterase from Bacillus stearothermophilus
was attached through its amino groups to a glyoxyl agarose
gel.67 Multipoint attachment increased the stability 30,000-
fold compared with 600-fold for one-point attachment. Ze-
olites have been used as supports for cutinase68 and
trypsin.69 A copolymer of N-isopropylacrylamide and N-
acryloxysuccinimide was used to immobilize -chy-
motrypsin as a material that dissolved below 35.5°C. and
precipitated at temperatures higher than that. It was 83.5%
as active as the free enzyme initially. Eighty percent of this
activity remained after nine precipitation–dissolution cy-
cles.70 Because the cost of immobilization can be a major
factor in industrial catalysis, cheaper methods are being
Biocatalysis and Biodiversity
sought. In one method, -glucuronidase immobilized on
the oil bodies of Brassica napus was as active as the free
enzyme.71 (Other immobilization methods were described
in Chap. 5.)
3. Biocatalysis at High Concentrations
One of the limitations of biocatalysis is that many reactions
must be run in dilute media. Stepwise addition of the sub-
strate and continuous removal of the product can help, as
mentioned earlier. However, sometimes this is unneces-
sary. The enzymatic hydrolysis of acrylonitrile produces
acrylic acid at 390 g/L.72 Some enzymes can be produced
by solid-state fermentations.73 Kluyvereromyces lactis pro-
duces -galactosidase when grown on corn grits or wheat
bran moistened with deproteinized milk whey. An acid
protease has been produced by Rhizopus oligosporus
grown on rice bran. Sugar beet pulp has also been used as
a substrate for the production of enzymes. An ento-
mopathogenic fungus for the control of insects, Metarrhiz-
ium anisopliae, has been grown on rice bran and rice husk.
Solid-state fermentation offers superior enzyme productiv-
ity, process simplicity, lower energy needs, lower waste
output, and ease of recovery of the product. Occasionally
the enzyme is just extracted with water. The process can be
used to upgrade agricultural wastes, such as wheat bran, ap-
ple pomace, corn stalks, and mussel-processing wastes to
products such as ethanol and citric acid.74 It is akin to rais-
ing edible fungi on an old log.
A lipase has been used to convert solid triolein (glycerol
trioleate) to the monooleate by treatment with glycerol at
8°C.75 Other lipases have been used in the hydrolysis and
transesterification of oils, as well as in the esterification of
fatty acids without solvents.76 Peptides can be produced
from eutectic mixtures of amino acid derivatives with the
addition of a small amount of solvent.77 Immobilized sub-
tilisin and thermolysin were used with 19–24% water or an
alcohol to produce polypeptides. Subtilisin on celite (a di-
atomaceous earth) was used to convert a mixture of L-
phenylalanine ethyl ester and L-leucinamide containing
10% triethyleneglycol dimethyl ether to L-phenylala-
nineleucinamide in 83% yield. Addition of 30% 2:1
ethanol/water reduced the time needed from 40 to 4 h. The
enzyme could be used three more times. These reaction
mixtures contained 0.13–0.75 g peptide per g reaction mix-
ture compared with 0.015–0.035 when the reaction was
9.3
245
carried out in solution. The small amount of solvent used
could probably be recovered for recycle by vacuum distil-
lation. This method may find wider use whenever the en-
zyme is not inhibited by the substrate and product. With the
advent of enzymes with greater thermal stability more
solids that melt on heating will become possible substrates.
Peptides have also been made with thermolysin in solid-to-
solid reactions in water, in over 90% yield.78 For this to
work, it may be necessary for the reactants to have a very
slight solubility in the water. After removal of the dipeptide
by filtration, the filtrate containing the enzyme might be
used in another run.
Solid enzymes have been used as fixed bed catalysts
with vaporized substances.79 As an example, allyl alcohol
has been oxidized to acrolein with aldehyde dehydrogenase
(9.3).
No solvent is needed. The dry enzyme is more stable to
heat than it would be in water. Mass transfer is improved
over a reaction in water. There is no need to immobilize the
enzyme. The process can be continuous. As more thermally
stable enzymes are found, this method will be applicable to
more substrates. It may also be possible to operate under a
partial vacuum to increase the range of substrates.
4. The Use of Enzymes in Organic Solvents
Our overall goal should be to reduce the use of organic sol-
vents. However, their use can overcome some problems
that are otherwise difficult to handle. The use of organic
solvents with enzymes allows water-sensitive compounds
or substrates that are difficulty soluble in water to be
used.80 Thermal stability is improved. Water-dependent
side reactions are suppressed. There is a shift to synthesis
over hydrolysis. There are some problems: Proteins are
usually insoluble in many organic solvents. Organic sol-
vents often inhibit the enzymes. The rates of the enzymatic
reactions usually drop dramatically in the shift from water
to organic solvents. A trace of water, at least part of a
monomolecular layer on the enzyme must be present, al-
though, in at least one case, methanol can be substituted for
it.81 Workers usually examine the amount of water needed
for optimal results. The use of cross-linked enzyme crystals
to circumvent some of these problems was discussed ear-
lier. The rate when they are used can be as high as in water.
When these are used in aqueous acetonitrile, the rate can be
increased 100-fold by adding a buffer of a suitable acid (for
246 Chapter 9

example, p-nitrophenol, phenylboronic acid, or triphenyl-

acetic acid) and its sodium salt.82 A solid-state buffer of ly-
sine plus lysine hydrochloride increased the activity of im-
mobilized substilisin in transesterifications run in hexane
or toluene.83 Subtilisin and chymotrypsin showed greater
activity in polar organic solvents when they were treated
with an aqueous buffer, silica, and 1-propanol, then used
without drying.84 The catalytic activity and enantio-
selectivity of Candida antarctica lipase in toluene im-
proved when it was used with an amine, such as triethyl-
amine.85 The use of supercritical (sc) carbon dioxide as a
medium, as described in Chap. 8, also overcomes some of
the problems in the use of organic solvents. A variety of
other approaches are being tried to remove these limita-
9.4
tions; but before examining them, the use of two-phase sys-
tems in which only one is organic will be covered.
Enzymes can be used in reverse micelles.86 In one case,
monomer is then polymerized with other acrylic
-galactosidase was encapsulated by bis(2-ethylhexyl)
monomers. Some of these conjugated enzymes can be used
sodium sulfosuccinate (a surfactant) and lecithin in isooc-
without solvent (e.g., in the transesterification of triglyc-
tane. The lecithin kept the enzyme from going into the bulk
erides at 58°C).
aqueous phase. (Surfactants can be used to make enzymes
Acetylation of horseradish peroxidase increased its half-
soluble in organic solvents.) It was used in the hydrolysis
life at 65°C fivefold and made it more tolerant to dimethyl-
of a galactose ester with the product being separated con-
formamide, tetrahydrofuran, and methanol.91 Chymo-
tinuously with centrifugal partition chromatography to give
trypsin is more active in organic media when immobilized
an 85% conversion in 5 h. Two-phase cultures can over-
than when it is just suspended.92 The selectivity of enzymes
come the problem of toxicity of the product or substrate to
in organic media can vary with the solvent.93 The transes-
the enzyme.87 Styrene has been converted to its epoxide
terification of racemic 1-phenylethanol with vinyl butyrate
with 95% or more enantioselectivity using xylene oxyge-
using subtilisin gave the best enantioselectivity in dioxane
nase in E. coli in such a system. Such extractive biocon-
(61%) and the least in N-methylacetamide (3%). Pretreat-
version has been used with animal cell cultures where one
ment of a lipase from Candida rugosa in isopropyl alcohol
phase contains aqueous polyethylene glycol and the other
increased the activity slightly and the enantioselectivity by
aqueous dextran. The bacterium Serratia macrescens has
more than tenfold in the resolution of ester 9.5.94 The R
been used to produce a chitinase in a two-phase system of
isomer had 93.1% enantiomeric excess (ee); the S isomer
2% aqueous polyethylene glycol (molecular weight
94.4%.
20,000, top phase) and 5% dextran in water.88 The cells re-
Surfactants can be used to solubilize enzymes in organic
main in the top phase. The enzyme is harvested by replac-
media and increase their activity.95 Ion pairing of -chy-
ing the lower phase to prevent back inhibition. -Galac-
motrypsin with bis(2-ethylhexyl) sodium sulfosuccinate
tosidase has been produced by E. coli in a two-phase
gave near-aqueous activity in a transesterification in isooc-
system of polyethylene glycol–aqueous phosphate.89 Some
tane.96 Enzymes can also be coated with lipids to make
of the cells were disrupted by ultrasound to release the en-
them soluble in organic solvents.97 The precipitate from
zyme to the top layer for harvest. The cells remained in the
mixing aqueous solutions of the two was lyophilized. It
bottom layer. The culture was run intermittently by adding
was soluble in benzene, ethyl acetate, isopropyl ether,
new top phases.
Bioconjugation of polyethylene glycol with enzymes in-
creases their thermal stability at the same time it increases
their solubility and activity in organic solvents.90 The at-
tachment can be accomplished in a variety of ways. The
reagents shown in 9.4 can react with amino groups in the
proteins.
Another method is to attach a polyethyleneglycol with
an acrylate on one end to the enzyme. The resulting 9.5
Biocatalysis and Biodiversity
9.6
ethanol, and dimethylsulfoxide. The lipid used (a surfac-
tant) is shown (9.6)
About 150 lipid molecules were present per 1 of en-
zyme. It was used to esterify 1-phenylethanol with lauric
acid in isooctane, giving 95% conversion in 2 h. A lipid-
coated lipase has also been used to esterify lauric acid with
glycerol in sc carbon dioxide with 90% conversion.98 Cata-
lase with less than 5% of its surface amino groups modified
by the nonionic surfactant 9.7 had a higher activity in 1,1,1-
trichloroethane than when the enzyme was conjugated with
polyethylene glycol.99
Crown ethers also enhance the activity of enzymes in or-
ganic solvents.100 The enzyme is lyophilized in the pres-
ence of the crown ether before use. -Chymotrypsin
treated in this way with 18-crown-6 was 640 times as ac-
tive in transesterification of amino acid esters as the un-
treated enzyme. However, the rate was still 50 times lower
than in water. The use of surfactants to improve activity in
organic solvents seems preferable because of a greater rate
increase. They also avoid the toxicity and expense of the
crown ethers. The cross-linked enzyme crystals also offer a
way to obtain reasonable rates in organic solvents.
Another way to improve on the rates in the presence of
organic solvents has been pioneered by Arnold and co-
workers.101 They carried out the directed evolution of a p-
nitrophenylesterase by random mutagenesis and screening
plus pairwise gene recombination. The improvement in
activity in one generation was not large. However, by car-
rying positive mutants through four generations they de-
9.7
247
veloped an enzyme that performed as well in 30% aqueous
dimethylformamide as the wild type did in water. The
method can be used to evolve thermally stable enzymes
and even to some that can carry out reactions not found in
nature. As few as four amino acid substitutions can convert
an oleate 12-desaturase to a hydroxylase, and as few as six
can carry out the opposite transformation.102
5. Extremophiles
Extremophiles are organisms, usually Archaea, that grow
normally under extreme conditions of heat, cold, salt, pres-
sure, anoxia, or pH.103 They live wherever there is water, to
depths of 4.2 km and temperatures up 110°C. This includes
deep sea hydrothermal vents, hot springs, Antarctica, salt
lakes, piles of sulfide minerals, sewage sludge, and such.
Their enzymes are sometimes called extremozymes. The
use of such enzymes tolerant of high temperatures could
speed up many reactions. Salt tolerance may translate into
better tolerance of organic solvents. Use of the high-tem-
perature enzymes with foods would not require a separate
sterilization step to remove unwanted bacteria. Use of en-
zymes adapted to cold104 could allow processing of food to
modify flavor and to tenderize meat without loss of nutri-
ents.105 Much energy might be saved if cold-adapted en-
zymes could be used in detergents to clean effectively in
water at room temperature.106 An understanding of how
these extremozymes tolerate such environments may lead
to ways to stabilize ordinary enzymes to extreme condi-
tions.107 Several hyperthermophilic enzymes,108 with opti-
mal temperatures of 95–110°C, have been purified. These
include hydrolases, oxidoreductases, dehydrogenases, hy-
drogenases, DNA polymerase, and glucose isomerase.
The upper limit on thermal stability of enzymes may be
about 120°C.109 Conformational stability and resistance to
the usual denaturation mechanisms must be present. The
aldehyde ferredoxin oxidoreductase from Pyrococcus fu-
riosus (which has an optimal growth temperature of 100°C)
has a lower surface area/volume ratio and greater than the
usual number of salt bridges between acidic and basic
amino acids.110 The enzyme contains tungsten. A protease
from Bacillus stearothermophilus that had optimum activ-
ity at 60°C was converted to one operable at 100°C by in-
troducing modifications that increased its rigidity.111 This
involved introduction of a disulfide bridge and substitution
of six of the enzyme’s amino acids by site-directed muta-
genesis, including glycine for alanine and alanine for pro-
line. It is amazing that protein monolayers applied to glass
spheres or other surfaces by the Langmuir–Blodgett tech-
nique are stable to 150–200°C.112
The complete gene sequence of 1.7 million base pairs of
248
the archaean Methanococcus jannaschii has been deter-
mined.113 The microorganism grows at about 100°C, using
only inorganic compounds and emitting by-product
methane. Pyrolobus fumarii grows at 90–113°C at vents in
the mid-Atlantic ridge using sulfur compounds and hydro-
gen.114 It needs no organic matter or oxygen to live. A re-
combinant xylanase from Thermatoga maritima was ac-
tive—over several hours at 100°C—in removing lignin and
sugars at pH 3.5–10.115 It may be useful in the enzymatic
pulping of wood. Two enzymes from thermophilic bacteria
convert glucose to gluconic acid and hydrogen with 100%
efficiency.116 No carbon dioxide is formed. This may be
useful in producing hydrogen fuel, if uses for large amounts
of gluconic acid can be found. Most hydrogen is produced
from natural gas now, rather than by electrolysis of water.
Hydrogen from glucose could be used in an ammonia plant.
The search for cold-adapted enzymes has involved bac-
teria from soils on mountain tops,117 salmon intestines,118
and whales rotting deep in the ocean.119 Enzymes from
these sources have greater flexibility and lower thermal sta-
bility. A bacterial lipase from Psychrobacter immobilis had
very little arginine compared with lysine, a low content of
proline, a small hydrophobic core and a very small content
of salt bridges.120 Comparison of the lactic dehydrogenases
of Anarctic fish with other fish showed that the active site
had not changed, but the surrounding structures were more
flexible.121
Microorganisms that grow under the high pressures of
the deep sea can be more resistant to organic solvents.122 A
strain of Pseudomonas putida from the deep sea tolerated
50% toluene. Microbial systems from deep basalt aquifers
(1000 m deep) exist on hydrogen plus water containing
some carbon dioxide.123 Other microbes are found in sedi-
ments hundreds of meters below the floor of the Pacific
Ocean and in granite several kilometers below the surface
in Canada and Sweden. Halophilic archaeans accumulate
inorganic ions at concentrations greater than those in the
environment (in places such as the Great Salt Lake in Utah
and the Dead Sea in Israel), whereas halophilic bacteria ac-
cumulate small osmoprotectants, such as glycerol.124
Halophilic enzymes require high salt concentrations (1–4
M) for stability and activity. A salt-loving bacterium (an
Altermonas) from a hot spring in western Utah is able to
neutralize nerve gases without formation of any toxic
by-products.125 Extremophiles may be useful in
bioremediation.
The bacterium Deinococcus radiodurans is able to resist
intense ionizing radiation (500,000–3 million rad).126 A
human would die with less than 500 rad. This tolerance
may have resulted from evolution to resist severe dehydra-
tion. Plants that have evolved to be dried down, then re-
Chapter 9
vived by water often contain the sugar trehalose (-D-glu-
copyranosyl-1,1--D-glucopyr anoside).127 It protects in-
sects, plants, and others from dessication, high osmolarity,
frost, and heat.128 It produces a stable glassy state that en-
ables the proteins to retain their native conformations and
suppresses aggregation of denatured proteins. It can be
made enzymatically from maltose.129 Addition of trehalose
before drying can stabilize invertase,130 as well as enzymes
that cut DNA.131 Addition of trehalose can allow reactions
to be run at higher temperatures (e.g., reverse transcriptase
reactions that are 20 times faster at 60°C than at ambient
temperature).132 Combining this with thermophilic en-
zymes may allow long-term storage of dry enzymes with-
out refrigeration. A combination of diethylaminoethyldex-
tran and a polyol kept an alcohol oxidase active for 2 years
in the dry state, whereas without these additives it lost ac-
tivity in a month at room temperature.133 A 2-M solution of
xylitol made -galactoside 10,000 more stable to high
pressure.134 Resistance to high pressure will become more
important as more foods are sterilized in this manner.
A -glucosidase from Pyrococcus furiosus has been
used to make glucoconjugates at 95°C for 15 h.135 Some
extremozymes are already in commercial use.136 A DNA
polymerase from Thermus aquaticus, found in a hot spring
in Yellowstone Park in Wyoming, is used in the poly-
merase chain reaction. The reaction was not practical for
widespread use until the thermophilic enzyme was found.
ThermoGen, Inc. (now part of Medi Chem) (Chicago, Illi-
nois) offers a series of esterases derived from thermophilic
organisms, some of which have optimal activities at 65 to
more than 80°C.137 They have a greater tolerance for or-
ganic solvents than the usual enzymes. Diversa (San Diego,
California) uses a somewhat different approach to the re-
covery of extremozymes from extremophiles.138 Ther-
mophilic organisms can be difficult to culture. The com-
pany bypasses this step by isolating the DNA from a
mixture of microorganisms, then cutting it into fragments,
which are cloned in another bacterium, such as E. coli. The
expression products of several clones are pooled and
screened for activity robotically. A lead that is found can be
optimized by random DNA mutagenesis. They now sell
kits of glycosidases, lipases, aminotransferases, phos-
phatases, and cellulases, each of which may contain up to
ten recombinant enzymes. (For more on genetic engineer-
ing, see the following Sec I.F.)
6. Catalytic Antibodies
An antibody formed in an animal in response to a model
compound for the transition state of a desired reaction may
serve as a catalyst for that reaction. It is hoped that these cat-
Biocatalysis and Biodiversity 249

alytic antibodies will function in the same way as natural en-

zymes.139 Reactions catalyzed by them include hydrolysis
of esters, opening of epoxides by hydroxyl groups,
Diels–Alder reactions, oxy-Cope reactions, cationic cy-
clization, elimination of hydrogen fluoride to form unsatu-
rated ketones, and aldol reactions.140 Antibody aldolases are
much more tolerant of varied structures than natural en-
9.8
zymes.141 Usually, the rate of the catalyzed reaction has
been relatively slow compared with catalysis by enzymes.
In one Diels–Alder reaction the rate enhancement was 2618 acylation, halogenation, esterification, hydrolysis, forma-
times. Occasionally, the rates do rival those of enzymes. A tion of amides, nitriles, and others. A few examples from
study of mutants of a catalytic antibody for the hydrolysis of the recent literature will be given to illustrate the nature and
p-nitrophenyl esters produced one that increased the rate an scope of the reactions.
additional 100-fold.142 The most active antibodies are ones
that increased the rate of hydrolysis of p-methylsul- 1. Oxidation and Reduction154
fonylphenyl esters by a factor of 100,000 and aldol reac- Aromatic compounds can be converted to vicinal glycols
tions by a factor of 2.3  108.143,471 The application of com- (9.8).155
binatorial chemistry to this field may provide substantial By proper choice of conditions various isomers can be
increases in rates.144 The catalytic antibodies may be most produced in up to 88% ee. Some aromatic compounds can
useful in catalyzing reactions for which there are no suitable be hydroxylated without loss of aromaticity 9.9.156
natural enzymes. An antibody produced in an animal can Phenols can be hydroxylated selectively (9.10), reac-
sometimes be transferred to a plant for production.145 tions that are hard to accomplish by chemical means.157
Side chains can be selectively oxidized (9.11).
7. Miscellaneous Techniques Laccase can be used to catalyze the oxidation of aro-
Some oxidoreductases require nicotine adenine dinu- matic methyl or methylol groups to the corresponding alde-
cleotide (NADH) as a cofactor.146 To use them in organic hydes (where R  Cl, alkoxy, nitro) by oxygen in the pres-
synthesis, as in the reduction of a ketone to an alcohol, it is ence of a benzothiazoline compound (9.12).158
necessary to have an efficient system to continuously re- Such transformations can also use 1-hydroxy-1-H-ben-
generate them. A common way is to include in the same re- zotriazole in place of the benzothiazoline.159 An alkane
action formic acid and formate dehydrogenase, the by- hydroxylase has been used to convert alkanes to alco-
product being carbon dioxide.147 The regeneration of the hols.160 Cholesterol can be oxidized to the ketone,
cofactor can also be done electrochemically with or with- cholestenone, with cholesterol oxidase in reversed mi-
out the addition of a hydrogenase.148 The use of whole or- celles of water in isooctane in 100% conversion.161
ganisms eliminates this need.
The ammonia that inhibited the growth of a mouse hy-
bridoma cell line was reduced about 50% by a pH gradient
across a hydrophobic microporous membrane.149 A com-
bined bioreaction and separation in centrifugal fields
(10,000 rpm) was used to keep dextransucrase at the top of
the supporting sucrose solution and the high molecular 9.9
weight dextran at the rotor wall.150 The rate of hydrolysis
of lactose by Lactobacillus bulgaricus was enhanced by ul-
trasound, which caused some of the -galactosidase to be
released from the cells.151 Ultrasonication somewhat in-
creased the rate of hydrolysis of sucrose by invertase.152

D. The Range of Biocatalysis

Enzymes and microbes can be used in a variety of ways in

organic synthesis.153 These include oxidation, reduction, 9.10
250
9.11
9.12
Aliphatic alcohols can be oxidized to the corresponding
carboxylic acid with Acetobacter aceti as long as the
amount of substrate is kept below the inhibiting level.162
The Baeyer–Villiger reaction of cyclic ketones can be car-
ried out with monooxygenases from P. putida (9.13) or A.
calcoaceticus, the former being preferred, because the lat-
ter is pathogenic.163
E-Coniferyl alcohol is converted into ()pinoresinol by
an oxidase in the presence of a guiding protein (9.14). In
the absence of the protein, the product is racemic.164
Enzymatic reductions are commonly used in asymmet-
rical synthesis (see Chap. 10). One of the most common
methods uses baker’s yeast (S. cerevisiae). The complete
9.13
Chapter 9
DNA sequence of 12 million nucleotides and 6000 genes
has been determined.165 It can be used to reduce -ke-
toesters in petrol plus a small amount of water to the S al-
cohol ester in 100% conversion with more than 98%ee.166
When only water is used as the medium, the enantioselec-
tivity is reduced greatly.167 In contrast with baker’s yeast
and Geotrichum candidum,168 which produce the S alco-
hols from the reduction of ketones, Yarrowia lipolytica
gives the R isomer, but in only moderate yields.169 Pichia
farinosa also produces the R isomer.170 (For more on the
preparation of single optical isomers, see Chap. 10.) Other
reductions can also be carried out with baker’s yeast as
shown in 9.15 for the quinoline oxide.171
Biocatalysis and Biodiversity
9.14
Sodium salts of carboxylic acids can be reduced to the
corresponding alcohols with Colletotrichum gloeospori-
oides in 70% yield.172 This is a reduction that is difficult to
carry out with the usual inorganic catalysts.
Lipases can be used to convert carboxylic acids to
peracids with hydrogen peroxide. The peracids are used in
situ for the oxidation of olefins, such as oleic acid, oleyl al-
cohol, and poly(1,3-butadiene).173
2. Preparation and Hydrolysis of Esters
One of the largest uses for lipases174 may be in the hydrol-
ysis and transesterification of oils and fats.175 The reactions
with enzymes are much gentler than the ones used today,
such as hydrolysis of a fat or oil in water at 150–260°C for
3–24 h. They are also less capital-intensive. Lipases can be
used for the hydrolysis and subsequent reesterification with
butyl alcohol of olive and rapeseed oils in 100% conver-
sion. An Aspergillus lipase hydrolyzed various fats and oils
in the presence of an aqueous buffer in 90–99% yields in
2–24 h.176 Much of the lipase remained in the emulsion at
9.15
251
the interface between the two layers. It could be recycled
repeatedly with no loss of activity in a week. The ability to
recycle is important because the cost of the enzyme is a
large factor in using this method. Lipases from oat cary-
opses (grains)177 and germinating rapeseed178 have been
suggested as being economically viable.
Biodiesel fuel can be made by the lipase-catalyzed alco-
holysis of oils such as rapeseed oil in over 90% conver-
sion.179 (The reaction is shown in 9.16 with triolein and
ethanol for convenience. Rapeseed oil also contains some
other fatty acids.)
Methanol is often used, but ethanol would be better be-
cause it can be made by fermentation. There is a problem
with the small amounts of stearates present crystallizing
out in cold winters. The use of isopropyl alcohol reduces
this problem. The other possibility is to crystallize it out at
the plant before it reaches the market. A better solution
might be to use a desaturase to introduce a double bond into
the stearate. Transesterification of rapeseed oil with 14.6%
lipase from C. rugosa (with no added solvent) took place in
1 h.180 When the level of enzyme was dropped to 0.3% the
252
9.16
reaction took 10 h. If the enzyme was immobilized, the use
of the large amount would not be a problem because the en-
zyme could easily be recycled. Removal of the glycerol
formed from the alcoholysis of fats and oils can improve
yields. When it was removed by adsorption on silica gel,
the yield was 98%.181
One fraction of the lipase from C. rugosa gave a 98%
yield in the esterification of oleic acid with 1-butanol.182
Polyunsaturated fatty acids have been esterified with
glycerol using an immobilized lipase to produce the tri-
ester in 95% yield.183 Esterification of fatty acids using a
silica-supported lipase gave 96–98% yields of ester when
a 4-A molecular sieve was used to remove the water
formed in the reaction.184 Another way to remove the wa-
ter continuously is to operate in a partial vacuum (0.7 bar
at 50°C), the yield being 96% in one case.185 Lauryl
oleate has been prepared in 85% yield without solvent us-
ing a fungal lipase on cellulosic biomass together with a
molecular sieve to pick up the by-product water.186 Im-
mobilized lipases are used in the commercial production
of isopropyl myristate, isopropyl palmitate, and 2-ethyl-
hexyl palmitate.187
Hollow-fiber membrane reactors with immobilized li-
pases have been used for the continuous hydrolysis of
triglycerides188 and in the esterification of fatty acids.189
There was no deactivation of the enzyme in the former
case in 16 days. In a comparable run in solution, the en-
zyme lost 80% of its activity in 2 days of operation. The
latter case used dodecanol and decanoic acid in hexane to
give the ester in 97% yield. The half-life of the immobi-
lized enzyme was 70 days. The integration of reaction and
separation can decrease product inhibition, increase selec-
tivity, shift equilibria, and reduce the number of down-
stream operations.190
Mono- and diglycerides are important food emulsifiers.
They can be made enzymatically by the glycerolysis of fats
and oils.191 The reaction can be run continuously in a mem-
brane reactor with an enzyme half-life of 3 weeks at 40°C.
Higher concentrations of glycerol can be used if silica is
present to prevent blockage of the enzyme by glycerol.192
Depending on the conditions and lipase chosen for transes-
terifications with ethanol, the product can be the 2-mono-
Chapter 9
glyceride,193 the 1,2-diglyceride,194 or the 1,3-diglyc-
eride.195 (The chemical route to monoglycerides involves
temperatures of 240–260°C.) Biosurfactants can be made
in this way.196 They can also be made by the enzymatic re-
action of long-chain fatty acids with sugars.197
Enzymes can be used to selectively hydrolyze only one
of two ester groups in a molecule. An esterase from Pseu-
domonas putida was used to hydrolyze dimethyl adipate
to more that 99% half ester.198 Pig liver esterase was used
to hydrolyze dialkyl phthalates to the monoesters in
84–93% yields in 1–13 h.199 A porcine pancreatic lipase
was used to hydrolyze linear diol diacetates to the
monoacetates in 79–95% yields.200 Esters have been pre-
pared from 12-hydroxystearic acid and C8–C18 alcohols in
82–90% yields without esterification of the 12-hydroxy
group, by using an immobilized lipase from Rhizomucor
miehei.201 Ricinoleic acid, which differs only by having a
cis-9-double bond, formed oligomers with an immobi-
lized lipase from C. rugosa.202 These were much less col-
ored than the ones made by the commercial process,
which is done at 200°C.
Since esterification is a reversible reaction, enzymatic
esterifications in organic solvents often employ vinyl esters
of fatty acids.203 The by-product vinyl alcohol isomerizes
to acetaldehyde (9.17); which cannot participate in the
back reaction.
Because some enzymes are deactivated by acetalde-
hyde, the variant in 9.18 in which the by-product is ethyl
acetate, has been developed as an improvement.204
(The deactivation is due to formation of Schiff bases
with the -amino group of lysine residues.205) Acyl car-
bonates can be used (9.19) in the same way.206
2,2,2-Trifluoroethyl esters can also be used. In one case,
N or O acylation depended on the solvent (9.20).207
Monoglycerides can be made by treatment of the vinyl
ester of a fatty acid with glycerol (without solvent) in
100% conversion.208 A lipase from Penicillium roquefor-
tii has been used to react unsaturated fatty acid vinyl es-
ters with glycerol to give more than 95% selectivity to
1,3-diglycerides in 85% yield.209 Diols can be converted
selectively to monoacetates.210 An example is given in re-
action 9.21.
Biocatalysis and Biodiversity 253

9.17

9.18

9.19

9.20

9.21
254
9.22
3. Preparation of Acids, Amides, and Nitriles
The commercial preparations of acetic, citric, lactic, and
malic acids were discussed earlier in this chapter. There are
also a number of other carboxylic acids that can be pro-
duced by biocatalytic methods.
Genetically engineered E. coli has been used to convert
glucose from corn into succinic acid (20–50 g/L).211 Suc-
cinic acid can be converted, in turn, by known methods into
1,4-butanediol, tetrahydrofuran, and N-methylpyrrolidone,
all of which are valuable commercial chemicals. The pro-
cess for succinic acid is said to be 20–50% cheaper than
other routes. A full-scale plant is planned. Glycolic acid
can be oxidized to glyoxylic acid microbially in 85%
yield.212 The catalyst could be recovered and reused
30 times. The product was used to prepare N-(phospho-
nomethyl)glycine (9.22) (an herbicide known as gly-
phosate).
Glycine has been converted into L-serine by reaction
9.23 with formaldehyde (a carcinogen) using E. coli.213
Limed straw and bagasse (the residue after the juice is
pressed from sugarcane) can be fed to ruminant animals.214
These can replace corn, which requires large amounts of
fertilizer, herbicides, and insecticides, that can lead to con-
tamination of groundwater. Alternatively, it can be treated
with rumen bacteria in an anaerobic fermentor to produce
acetic, propionic, and butyric acids. Salts of these acids can
be pyrolyzed to produce ketones. These can then be re-
9.23
9.24
Chapter 9
duced to alcohols with hydrogen. Such syntheses allow the
conversion of unwanted wastes, such as municipal solid
waste, sewage sludge, and agricultural wastes, to valuable
chemicals or fuels, instead of the wastes ending up in an in-
cinerator or a landfill. The process replaces nonrenewable
petroleum as a source of these chemicals.
Propionic acid can also be made from the hemicellu-
loses in wood.215 These have few other uses. Steam-ex-
ploded Populus tremuloides was hydrolyzed enzymati-
cally, then the hydrolysate treated with Propionibacterium
acidipropionici to produce 18 g/L of propionic acid. Be-
cause this organism is inhibited by the product, various
methods have been developed to remove it as formed. Use
of ditridecylamine in oleyl alcohol with a hollow-fiber
membrane gave a higher yield, final product concentration,
and purity, at the same time that the production of acetate
and succinate were reduced in a run of 1.5 months.216 The
acid was recovered with aqueous sodium hydroxide using
a second hollow-fiber membrane.
Long-chain unsaturated fatty acids, which are of interest
for good health,217 can also be produced biocatalyti-
cally.218 Arachidonic acid (9.24) has been produced by
growing the fungus, Mortierella alpina, on a mixture of
glucose and potatoes.219 -Linolenic acid (9.25) has been
produced by growing Cunninghamella echinulatum on
starch plus potassium nitrate or urea.220 The eicosapen-
taenoic (9.26) and docosahexaenoic (9.27) acids from fish
oils help prevent heart attacks. Much effort has been di-
Biocatalysis and Biodiversity
9.25
9.26
9.27
rected toward preparing them more conveniently from al-
gal, Antarctic sea ice bacteria, and fungal cultures.221 The
use of bacterial cultures may be the best, because they are
often easier to culture than algae and tend to produce less
complex mixtures of fatty acids.
Desaturases are involved in the biosynthesis of these
acids. It may be possible to use such enzymes for the com-
mercial conversion of saturated fats to unsaturated ones.
Surplus butterfat and tallow might be converted into more
nutritious oils in this way. (Saturated fats in the diet have
been implicated in heart problems.)
A Flavobacterium sp. can be used to hydrate linoleic
acid to 10-hydroxy-12(Z)octadecenoic acid, an analogue
of ricinoleic acid.222 Ricinoleic acid (12-hydroxy-9(Z)oc-
tadecenoic acid) from castor oil is important in the prepa-
ration of paints and varnishes.223 Cryptococcus neofor-
mans can convert n-pentadecane to the corresponding
-
-dicarboxylic acid (HOOC(CH2)13COOH).224 formed in situ. Candida antarctica lipase can also be used
Toluene can be converted to 4-hydroxybenzoic acid
9.28
9.29
255
(9.28), a monomer used to prepare polyesters for use at
high temperatures, with 99% selectivity by P. putida.225
Further work is needed to speed up the reaction before it
can be used commercially. Pyrrole-2-carboxylic acid can
be made from pyrrole and carbon dioxide (9.29) using
Bacillus megaterium.226 It should be possible to improve
the 52% yield by continuous removal of the product as
formed.
An enzymatic Friedel–Crafts reaction has been carried
out with polyprenyl transferase (9.30) where n  1, 12).227
Triglycerides can be converted to the corresponding
amides using C. antarctica, with ammonia in tert-butyl al-
cohol.228 Olive oil gave a 90% yield of oleamide in 72 h at
60°C. Industrial reactions of this type are run at 200°C. The
enzyme can also be used to convert oleic acid to oleamide
in 90% yield in tert-amyl alcohol containing two equiva-
lents of n-butyl alcohol. The intermediate butyl ester is
to prepare monoesteramides from dimethyl succinate
(9.31).229
The corresponding imide can be formed if the medium
is hexane. Amines can be protected as their allyl carba-
mates by formation with diallyl carbonate and a lipase
(9.32).230
Amides can be made by the enzymatic hydrolysis of ni-
triles. Nitto Chemical Industry of Japan uses Rhodococcus
rhodocrous to prepare acrylamide from acrylonitrile
256
9.30
9.31
(9.33).231 Lonza is using it for the hydrolysis of 3-cyanopy-
ridine to niacinamide in a plant in China.
Depending on the microorganism, the product of hy-
drolysis of a nitrile may be the amide or the carboxylic acid
(9.34).232 Rhodococcus spp. have also been used to hy-
drolyze only one of two nitrile groups in aromatic dinitriles
in 86% yield.233 Rhodococcus rhodochrous has been used
to hydrolyze aliphatic dinitriles, such as adiponitrile, to
9.32
9.33
Chapter 9
mixtures of mono- and dicarboxylic acids.234 Pseu-
domonas chlororaphis has been used to convert adiponi-
trile to 5-cyanovaleramide with 96% selectivity at 97%
conversion.235 This is a significant improvement over the
best chemical process.
The enzymatic hydrolysis of the amide in penicillin G
(9.35) has replaced a cumbersome multistep chemical syn-
thesis in methylene chloride that produced waste salts.236
Biocatalysis and Biodiversity
9.34
9.35
The reaction can be run in a polysulfone reactor with con-
tinuous removal of the product amine in the permeate.237
The use of an expandase to convert penicillins to
cephalosporins (9.36) also replaced a more expensive mul-
tistep chemical synthesis.238 Penicillin acylase has also
been used to remove phenylacetyl protecting groups from
amines in the synthesis of oligonucleotides.239
9.36
257
Hydroxynitrile lyases can be used to make cyanohydrins
(9.37) in 80–100% yields.240
4. Compounds with Two or More Hydroxyl Groups
Glycerol can be produced in 70–90% yields by a triose phos-
phate-deficient mutant of S. cerevisiae.241 It can also be pro-
duced by raising halophytic microalgae. If the preparation of
258
9.37
biodiesel fuel by the alcoholysis of rapeseed oil comes into
widespread use, there may be a surplus of glycerol. Various
groups are trying to find uses for it. It can be converted to
propionic acid with a Propionobacterium in a membrane re-
actor without the formation of any acetic acid.242 It has also
been converted to 3-hydroxypropionaldehyde by Klebsiella
oxytoca.243 This product can be converted to an important
monomer, acrylic acid, by dehydration and oxidation. Glyc-
erol has also been converted to 1,3-propanediol, which can
be used to make poly(trimethylene terephthalate).244 The
continuous fermentation with K. pneumoniae produced the
product in 80–96% yield (35–48 g/L). The continuous cul-
ture was two to three and a half times as productive as a batch
culture. An analogue of ethylenediaminetetraacetic acid
(EDTA), which may be cheaper to produce, has been made
by the action of Amycolotopsis orientalis on a mixture of
glycerol and urea (9.38).245
The use of metabolic engineering to bolster some path-
ways and eliminate others has made it possible to produce
both 1,3-propanediol (by Klebsiella pneumoniae) and 1,2-
propanediol (by Thermoanaerobacterium thermosaccha-
rolyticum) from sugars.246 duPont and Genencor have
worked out a process to make 1,3-propanediol from hy-
drolyzed cornstarch using a recombinant microorgan-
9.38
9.39
Chapter 9
ism.247 It has been known for some time that this polymer
has good properties, but its commercial production has
been delayed for want of a good inexpensive source of 1,3-
propanediol. Degussa is planning to make the diol by hy-
dration of acrolein followed by reduction.248 The same 3-
hydroxypropionaldehyde can be obtained from glycerol by
fermentation. Shell has announced a plant to make the diol
by continuous ethylene oxide hydroformylation.249 The
raw materials will probably be derived from petroleum, al-
though they could be derived from renewable sources. The
ethylene could be produced by dehydration of ethanol. The
synthesis gas could be made from biomass. The intermedi-
ate ethylene oxide is a carcinogen. Almost 3 billion lb of
1,2-propanediol is made each year from propylene oxide,
which is made, in turn, from propylene derived from
petroleum. It is used in unsaturated polyester resins, deic-
ing fluids, antifreeze, and such. It could be made from re-
newable resources such as sugars. Glycols can also be
made from epoxides using epoxide hydrolases.250
Carbohydrate synthesis usually involves selective pro-
tection of some groups, reaction of the others, then depro-
tection. The enzymatic aldol reaction can produce some
sugars without the need for any protecting groups.251 An
example is the preparation of 6-deoxy-L-sorbose (9.39).252
Biocatalysis and Biodiversity
9.40
Both starting materials were prepared enzymatically.
Genetically engineered bacteria have been used to convert
glucose to 2-keto-L-gulonic acid, eliminating four steps in
the synthesis of ascorbic acid (vitamin C).253
Cyclodextrins (see Chap. 5) can be prepared in one step
from starch using a recombinant enzyme based on a ther-
mophilic bacterium, a species of Thermoanaerobacter.254
Cyclodextrin glucanotransferase from Bacillus macerans
and other organisms can also be used.255
Many polysaccharides, such as agar, agarose, alginic
acid, and carrageenan, are extracted from marine algae.256
Controlled microalgal culture including genetic engineering,
species and strain selection, timing and method of harvest-
ing, drying and storage conditions, can give 15–20 times the
biomass of natural systems.257 These polysaccharides show
up in practically every food market as thickeners and stabi-
lizers for foods.258 They are common in fat-free foods. L-
Ascorbic acid (vitamin C), -carotene, glycerol, and do-
cosahexaenoic acid (needed in infant nutrition) can also be
produced by algae.259 The microalgae Chlorella and Spir-
ulina are sold as foods. Industrial-size photobioreactors that
use optical fibers to direct solar light are being developed.260
In Japan, macroalgae are cultured on nets for sale as foods.
5. Preparation of Aromatic Compounds
The carcinogen benzene (derived from petroleum) is the
starting point for many important industrial chemicals. The
syntheses often involve stringent conditions and may pro-
9.41
259
duce toxic by-products. The preparation of adipic acid for
the manufacture of nylon is an example (9.40).
In contrast, biological systems produce aromatic com-
pounds such as phenylalanine and tryptophan (9.41) under
mild conditions from renewable resources without the for-
mation of toxic by-products.
The pathway proceeds from glucose through shikimic
acid.261 Frost and co-workers have altered the pathways
shown in Fig. 9.1 to favor the desired aromatic com-
pounds.262 This has been done by genetically engineering
the microorganisms to cut out or reduce certain unwanted
pathways while enhancing others.263 It has been possible in
this way to convert glucose from corn into catechol, hydro-
quinone, adipic acid, gallic acid (3,4,5-trihydroxybenzoic
acid), and vanillin (4-hydroxy-3-methoxybenzalde-
hyde).264 The yield of phenylalanine has been doubled.
Some phosphoenol pyruvate is used to introduce the glu-
cose into the cell. An E. coli mutant has been found that
does not need this.265 It gave increased yields of pheny-
lalanine and tyrosine.
Indigo, the dye used to color blue jeans, can be made en-
zymatically by removal of the side chain of tryptophan to
give indole, which can be dihydroxylated enzymatically,
then oxidized with oxygen to indigo (9.42).
The present commercial route starts with the highly
toxic aniline and produces waste salts. An even “greener”
way to indigo would be to raise it as a crop as done in Colo-
nial America. A new commercial strain produces five times
more indigo than the usual plant.472
260 Chapter 9

Figure 9.1 Altered pathways for production of aromatic compounds from glucose (A) DAHP synthase; (B) DHQ synthase; (C) DHQ
dehydratase; (D) shikimate dehydrogenase; (E) quinate dehydrogenase; (F) DHS dehydratase; (G) protocatechuate decarboxylase; (H)
catechol 1,2 dioxygenase. Reprinted with permission of J.W. Frost.
Biocatalysis and Biodiversity
9.42
Many of these processes cannot compete with the chem-
ical routes used today. If total environmental costs of
global warming, natural resource depletion, waste disposal,
and such were included, more of them would be practical
today. Research continues to reduce their costs by increas-
ing yields, starting with waste biomass where both five-
and six-carbon sugars must be utilized and so forth.
6. Miscellaneous Applications
Most of the industrial applications of enzymes266 men-
tioned earlier have dealt with the production of fine chem-
icals or drugs.267 Several other large, or potentially large,
uses are described in the following.
Enzymes are now being used by the pulp and paper in-
dustry, at least experimentally.268 Ligninolytic fungi can be
used to remove lignin.269 Mutants that lack cellulases are
used. This can save 30% of the electrical energy and im-
prove paper quality. Phanerochaete chrysosporium is the
organism of choice. Lipases that hydrolyze triglycerides
are being used to control pitch in mills.270 Xylanases re-
duce the amount of chemicals needed for bleaching; in
some cases for a 25% saving in chemical costs. A ther-
mophilic xylanase from Dictyloglomus thermophilum
works optimally at 70–85°C, which makes it easier to fit
into mill operations. Another from Bacillus amyloliquefa-
ciens has optimal activity at 80°C, excellent stability at
50°C, and no cellulase activity.271 Cellulases used in con-
trolled ways can smooth fibers by removing fine fibrils, en-
261
hance drainage, and promote ink removal in repulping.272
Levanases can be used in combination with biocides for
improved control of slime in paper mills.273
Biofinishing of cotton and woolen fabrics with cellu-
lases, pectinases, and proteases is being used to remove
protruding fibers and to avoid chemical finishing agents
such as sodium hydroxide.274 The resulting fabrics are
smoother and softer, but do lose some tensile strength in the
process. Cellulases275 are also used in detergents to reduce
pilling of cotton fabrics.276 The wettability of poly(ethy-
lene terephthalate) fabrics is better improved with lipases
than with the conventional treatment with sodium hydrox-
ide.277 Fibers from kenaf, jute, hemp, and flax are stronger
when prepared with bacteria (30°C for 10 days) than when
the unwanted parts of the plants are removed chemi-
cally.278 Polyvinyl alcohol that is used to stiffen cotton dur-
ing weaving (a warp size) can be removed enzymatically in
1 h at 30–55°C, and the effluent fed to a conventional
wastewater treatment plant.279 Conventional desizing is
done at 80°C for 30 min. It would be better to dissolve the
size in water, then recover it for reuse by ultrafiltration.
Biomining involves the extraction of metal ions from
their ores.280 Low-grade ores of copper are piled on imper-
vious aprons and treated with sulfuric acid. The Thiobacil-
lus ferrooxidans that grows under these conditions con-
verts the copper sulfide to copper sulfate that drains off
with the sulfuric acid for recovery by electrowinning.
Twenty-five percent of all copper is produced in this way.
A combination of Thiobacillus ferrooxidans and T. thioox-
262
idans leached metals from fly ash from municipal inciner-
ators (recovering 81% Zn, 52% Al, 89% Cu, 64% Ni, 12%
Cr, 100% Cd).281 Although this is a way to recover the met-
als and detoxify the ash, it would better to recycle the ob-
jects containing the metals rather than putting them in an
incinerator. This system may also be applicable to the ash
from coal-burning power plants. Thermophilic bacteria
have been used at 50°C to recover 98% of the gold from
ores not amenable to cyanide leaching.282 Phosphoric acid
is usually obtained from calcium phosphate ore by treat-
ment with sulfuric acid. It can also be recovered at room
temperature using the gluconic acid and 2-ketogluconic
acids produced by Pseudomonas cepacia and Erwinia her-
bicola. For practical use, a way to recover and reuse these
acids must be found. A book on the environmental effects
of mining is available.283
Sulfur dioxide from electric power plants is a major
source of acid rain. Although much of this can be taken out
of the stack gas with the proper scrubbers, it would be de-
sirable to remove the sulfur from the coal before it is
shipped to the power plant. Inorganic sulfur, in the form of
pyrite (FeS2) can be removed by flotation of the ground
coal. The sulfur present in organic compounds is harder to
remove. Biodesulfurization of coal can be done with
Rhodococcus rhodocrous or Agrobacterium spp. without
loss of carbon.284 The sulfur in petroleum can be converted
to sulfuric acid by T. denitrificans, then removed by wash-
ing with aqueous sodium hydroxide or ammonium hydrox-
ide.285 Energy BioSystems of Houston, Texas has a pilot
plant using such a process.286 The Petroleum Energy Cen-
ter (Tokyo) is using a Paenibacillus sp. to reduce the sulfur
to less than 50 ppm.287 Current systems for the desulfur-
ization of petroleum use cobalt and molybdenum catalysts
with hydrogen at high temperatures. They do not remove
all of the sulfur. What is left contributes to acid rain and can
foul catalytic systems on the tail pipes of diesel engines.
Sulfate-reducing bacteria, such as Desulfovibrio desulfuri-
cans, have been used with anaerobic sewage sludge to re-
duce part of a sulfur dioxide stream to hydrogen sulfide.
This could then be combined with the rest of the sulfur
dioxide to produce elemental sulfur in a Claus plant.288
Pseudomonas putida cells, immobilized in calcium algi-
nate, have been used to convert minor amounts of hydrogen
sulfide in gas streams to elemental sulfur.289 The use of
bacteria to remove nitrogen from the nitrogen compounds
in petroleum is being studied.290 The hope is to obtain a set
of bacteria that will remove both nitrogen and sulfur in a
single treatment. One of the big advantages of renewable
energy sources, such as solar, wind, tidal, and hydropower,
is the absence of sulfur compounds.
The aqueous extraction of edible oils from oilseeds
works better when enzymes are used to hydrolyze struc-
Chapter 9
tural polysaccharides in the cell walls first.291 It is possible
to recover over 90% of the oil by boiling the ground,
treated seeds, then centrifuging and collecting the layer of
oil. Further work is needed to make the process more effi-
cient. Each oilseed species may require different enzymes.
The aqueous process may replace ones using hexane,
which is flammable. Extraction with supercritical (SC) car-
bon dioxide was discussed in Chap. 8. A cellulase–pecti-
nase combination helped the extraction of antioxidant phe-
nols from grape pomace (the waste left from making grape
juice).292
The fungus, Monascus purpureus, produces yellow, or-
ange, and red pigments of the polyketide type, which have
been used for coloring food in the Far East for cen-
turies.293 It can be grown on ethanol. These pigments in-
hibit the mutagenicity of the heterocyclic amines formed
by cooking meats at high temperatures. This may offer an
alternative to the use of synthetic food dyes, for which
safety concerns have been expressed. Some synthetic food
dyes have already been banned in the United States. One
strain of the red yeast produces not only the color, but
also a statin (a drug that lowers the level of cholesterol in
the blood).294
Biofiltration can be used to remove volatile organic
compounds, including odors, from waste air.295 Pseu-
domonas spp. can remove toluene, and Bacillus spp.,
ethanol. The process is suitable for use on food-processing
plants, public treatment works, and others, to control odors.
The cost can be quite a bit lower than that of incineration or
adsorption on carbon. A biofilter with Nitrosomonas eu-
ropaea immobilized in calcium alginate removed 97.5% of
ammonia from air.296
Bioremediation often uses bacteria.297 These are se-
lected from contaminated sites or engineered to degrade
common organic pollutants. Phytoremediation involves the
use of hyperaccumulating flowering plants to remove toxic
metal ions from the soil.298 Brassica juncea can accumu-
late selenium, lead, chromium, cadmium, nickel, zinc, and
copper. Thlaspi caerulescens can accumulate cadmium and
zinc. It can accumulate up to 25 g of zinc per kilogram. It
is being tested at the former zinc mine in Palmerton,
Pennsilvania. Tetraethyllead used to be made by duPont in
New Jersey across the river from Wilmington, Delaware.
The best plant found so far for removing the lead from the
ground is Ambrosia artemisiifolia (ragweed). (Many peo-
ple are allergic to the pollen of this plant.) More efficient
plants are being sought. The plants containing the metals
would be burned to recover the metals for reuse. A
Japanese process employs anaerobic bacteria to reduce the
level of selenium in industrial waste water to less than 0.1
ppm.299 The process may be suitable for selenium-contain-
ing water in the western United States where wildlife
Biocatalysis and Biodiversity
refuges have been contaminated, but the water would have
to be deaerated first.
Municipal or food-processing sludges can be converted
to single-cell protein for animal feed using thermophilic
bacteria, the product being sterilized by the heat in the pro-
cess.300 It is possible to remove 99% of the biological oxy-
gen demand, total dissolved solids, ammonia, nitrogen, and
phosphorus from wastewater by growing duckweed on it.
The plant can be harvested and sold for use as fertilizer. Pig
waste is a problem in the Netherlands, Iowa, North Car-
olina, and other areas. By running it through a series of
three reactors, anaerobic, aerobic (nitrification), and anaer-
obic (denitrification), the chemical oxygen demand was re-
duced 90%, ammonium ion 99.8%, and nitrate ion
98.8%.301 It is possible that methane could be generated at
the same time and used for power at the farm. The same
might be done with chicken waste in Delaware. Enzymes,
such as xylanases and proteases, are being used to improve
the digestibility of animal feeds.302 A large potential mar-
ket exists for the addition of phytase303 to the feeds to re-
-Hy-
duce the phosphorus content of the animal waste by about
30%.
E. Enzymatic Polymerization
Enzymatic polymerization and oligomerization can be used
to make polyesters, polypeptides, polysaccharides, poly-
mers from phenols, polymers from anilines, and many oth-
ers. This approach could lead to fewer side reactions,
higher regio- and stereoselectivity, under milder condi-
tions. Oligomeric polyesters can be prepared from lac-
tones. Caprolactone can be polymerized in bulk with li-
pases (9.43) to polymers with molecular weights of
7000.305
Other lactones and propylene carbonate (1,3-dioxane-2-
one) polymerized in the same way.306 Lactide (3,6-
dimethyl-1,4-dioxane-2,5-dione) polymerized in bulk with
a lipase to a polyester with a molecular weight of
126,000.307 Lyoprotectants, such as polyethylene glycol,
glucose, sucrose, and cellobiose, added before lyophiliza-
tion, enhanced the activity. When a small amount of vinyl
methacrylate is present in the polymerization, the product
9.43
263
is a macromonomer in which the hydroxyl group in the
foregoing formula has been converted to a methacrylate.
This underwent further polymerization with free radical
initiators. The hydroxycarboxylic acid corresponding to n
 10 was polymerized with Candida cylindracea lipase to
a polymer with a weight average molecular weight of
35,000.308
Polymers have been prepared from diols such as 1,6-
hexanediol with dimethyl esters of succinic, adipic, fu-
maric, maleic, isophthalic, and terephthalic acids using
lipases.309 The by-product methanol was removed with a
molecular sieve or with a nitrogen sparge. Number average
molecular weights up to 12,900 were obtained. Similar
polymerizations have been carried out using divinyl, bis(2-
chloroethyl), and bis(2,2,2-trifluoroethyl) esters.310 The
highest weight-average molecular weight, 46,400, was ob-
tained when the by-product alcohol was removed with a
vacuum. The reaction of divinyl adipate with triols, such as
glycerol, in the presence of a lipase also led to linear poly-
mers with molecular weights as high as 10,391.311
droxy esters have also been polymerized by lipases.312
Oligomeric polyesters with molecular weights of only a
few thousand are suitable for reactions with diisocyanates
to produce polyurethanes. Glucose has been reacted with
one end of divinyl sebacate in the presence of a lipase to
produce a vinyl monomer that gave poly(6-O-vinylseba-
cyl-D-glucose), with a number average molecular weight of
11,000 on polymerization with 2,2-azobisisobutyronitrile,
an initiator for free radical polymerization.313
Sucrose-1-acrylate has been prepared by the reaction of
vinyl acrylate with sucrose, using subtilisin.314 It can be
polymerized with free radical initiators in water to a poly-
mer with a number average molecular weight of 2.4 mil-
lion. It can also be copolymerized with acrylic acid. When
copolymerized with a cross-linking diacrylate, it produces
a copolymer that can pick up 1000 times its weight of wa-
ter. Such polymers are useful in diapers and seed treat-
ments. The usual superabsorbents derived from acrylamide
(a neurotoxin) do not work as well in salt solutions. Be-
cause the sugar acrylate polymers have no ionic groups,
they do not have this problem. Other sugar monomers are
shown in 9.44.315 The first was made using Candida
antarctica.
Disaccharide fluorides have been treated with cellulase
to produce cellulose, amylose, and xylan.316 A mutant
strain of Acetobacter xylinum produced cellulose that im-
parted higher tensile strength and superior properties to pa-
per than did cellulose from higher plants.317 An economi-
cal mass production technique has been devised for it.
Polyhydroxyalkanoates are produced by bacteria for
storage purposes.318 Monsanto (formerly Zeneca) for-
merly produced 1000 tons/yr of a random copolymer of 3-
264
9.44
hydroxybutyrate and 3-hydroxyvalerate by growing Al-
caligenes eutrophus on a mixture containing glucose and
propionic acid. The high cost of $15/kg for this
biodegradable polymer has limited its use. Growth of
Pseudomonas oleovorans on a mixture of n-octane and 1-
octene produces a poly(hydroxyalkanoate) that can be
cross-linked with an electron beam to a biodegradable
rubber.319 Attempts are being made to reduce the costs of
polyhydroxyalkanoates by the use of wastes as growth
media, and at the same time solving waste disposal prob-
lems. These include swine waste liquor,320 palm oil
waste,321 and alcoholic distillery wastewater.322 Another
way to reduce costs would be to transfer the necessary
genes to a crop plant that could be grown in a field. The
polyhydroxyalkanoates have been produced in transgenic
Arabidopsis plants. They have also been produced on an
experimental basis in poplar trees.323 The polymer was
extracted from the ground dry leaves with chloroform. It
is desirable to find a less dangerous solvent for the ex-
traction. It is possible that these methods will make it eas-
ier to replace some of the polyolefins that are in
widespread use. It is also possible to produce polyethy-
lene by polymerization of ethylene derived from ethanol
from fermentation. However, the polyethylene is not
biodegradable the way the polyhydroxyalkanoates are.
(For more on the production of polymers and other mate-
rials from renewable raw materials, see Chap. 12.)
Phenols can be converted to polymers by the action of
peroxidases and hydrogen peroxide (9.45).324
The goal is to prepare phenolic resins without the use of
formaldehyde (a carcinogen). Yields can be as high as
90–95%. The products from phenol and p-cresol are only
9.45
Chapter 9
partially soluble in dimethylformamide. Molecular weights
can vary from a few thousands up to 800,000.325 Enzymol
International (Columbus, Ohio) is commercializing the
process using a peroxidase from soybeans.326 Bisphenol A
gives soluble polymers when the hydrogen peroxide is
added in small portions every 15 min.327
It is not completely clear how these polymers will be
fabricated into useful articles. Phenol–formaldehyde resins
go through a soluble prepolymer stage that is cured to give
the final product. It is possible that soluble oligomers made
by the action of peroxidases on phenols could be cured in a
melt with diisocyanates, diepoxides, dianhydrides, or
bisoxazolines. A soluble monomer, prepared by the action
of horseradish peroxidase on 4(2-methacrylatoethyl)phe-
nol was cured with either light or 2,2-azobisisobutyroni-
trile.328 A soluble oligomer with a degree of polymeriza-
tion up to 12 has been prepared by polymerizing
hydroquinone with one hydroxyl group blocked with a
sugar, then removing the sugar by hydrolysis (9.46).329
Perhaps the process can be extended to natural phenolic
compounds to produce inexpensive products indepen-
dently of petroleum sources.
A poly(phenylene oxide) has been made by oxidation of
2,6-dimethylphenol with laccase and oxygen (9.47).330
General Electric polymerizes this phenol to a polymer of
high molecular weight using oxygen with a copper salt and
pyridine.
Aniline can also be polymerized by horseradish peroxi-
dase and hydrogen peroxide to electrically conducting
polymers.331 If run in the presence of sulfonated
polystyrene, this leads to a water-soluble doped polymer in
a one-pot, benign process. Horseradish peroxidase and hy-
Biocatalysis and Biodiversity
9.46
drogen peroxide convert p-aminobenzoic acid to a self-
doped, water-soluble electrically conducting polymer.332
The method also converts o-, m-, and p-phenylenediamines
to polymers.333
Tetraalkoxysilanes can be converted to polysiloxanes in
1 h at 20°C, using a siloxane polymerase from a marine
sponge.334 Many living organisms use such enzymes to
produce shape-controlled silica skeletons.
Enzymatic polymerization will have its greatest value
when it uses renewable raw materials to make, under mild
conditions, polymers that are biodegradable. It should
avoid toxic chemicals and toxic catalysts. Some polymers
that can be prepared in this way cannot be made by the
usual chemical methods.
F. Genetic Engineering
It is evident from the earlier discussion that genetic engi-
neering plays an integral role in the design of better biocat-
alysts. Over 60% of industrial enzymes are recombinant
products.335 The stability of subtilisin increased 1000 times
when a calcium ion-binding loop was deleted, then fol-
lowed by directed mutagenesis and selection.336 Blocked
metabolic pathways can allow desired products to accumu-
late (e.g., the food ingredients L-glutamic acid and citric
acid.337 Analogues of the antibiotic, erythromycin, have
been made in Streptomyces coelicolor containing a genetic
9.47
265
block.338 Putting the genes of one organism into another
can produce a recombinant organism that can convert both
glucose and xylose to ethanol, as mentioned earlier. Preg-
nenolone and progesterone have been produced from a
combination of sugars and ethanol in recombinant S. cere-
visiae.339 The sweet noncariogenic protein, monellin, has
been produced by recombinant Candida utilis.340
Plant biotechnology,341 as applied to field crops, has a
variety of goals. A few examples will illustrate some of
these. Antisense inhibition of polyphenol oxidase gene ex-
pression prevents discoloration of potatoes after bruis-
ing.342 A transgenic potato expressing a double-stranded
RNA-specific ribonuclease (from yeast) was resistant to a
potato spindle tuber viroid.343 Decaffeinated coffee has
been produced by silencing the gene for xanthosine N 7-
methyltransferase, which is involved in the production of
caffeine.344 Proteins in E. coli can be enriched in essential
amino acids, such as methionine, threonine, lysine, and
leucine.345 The work was done with cattle feed in mind, but
it should also be applicable to cereal crops in developing
nations where some people have protein-deficient diets.
This supplements the efforts of conventional breeding to
produce high-lysine corn for animal feed. Plant lipids can
be altered by genetic engineering.346 Lauric acid is usually
obtained from coconut oil. By putting the thioesterase gene
from the California bay tree (Umbellularia californica)
into rapeseed, a transgenic plant producing an oil that is
266
nearly 40% laurate has been obtained.347 Another route in-
volves the introduction of the gene for petroselenic acid
(the -6 isomer of oleic acid) into rapeseed. Ozone oxida-
tion of petroselenic acid gives lauric and adipic acids. The
latter is used in making nylon. Trees genetically engineered
to produce less lignin would be easier to pulp for paper.348
Only field tests will tell whether they will be more suscep-
tible to storm damage. They would have to be sterile so that
they do not hybridize with the same or related species lo-
cated nearby.
Efforts to modify the cotton plant aim to improve its re-
sistance to insects, herbicides, viruses, nematodes, and
stress.349 Seeds free of gossypol are also desired. Cotton
which expresses the natural insecticidal protein of Bacillus
thuringiensis was used in 61% of the cotton crop in the
United States in 2000.350 Calgene has engineered cotton to
produce melanin so that the brown or black fiber will re-
quire little or no dyeing.351 Further effort is being directed
toward red and blue fibers. This method eliminates a chem-
ical-dyeing operation that is often the source of contami-
nated wastewater. Agracetus has put bacterial genes for
polyhydroxybutyrate into cotton so that a hybrid fiber is
produced.352 The resultant fiber is an all-natural equivalent
of polyester–cotton blend fabrics.
Transgenic plants can lead to increased crop yields, re-
duced use of pesticides, and a shift to integrated pest man-
agement and conservation tillage.353 Field trials of trans-
genic plants in the United States in 1994 involved 41% for
herbicide resistance, 22% for insect resistance, and 18% for
improved product quality.354 Of the ones for herbicide tol-
erance, 45% were for corn and 24% for soybeans. For the
period 1987–1998, crops were modified genetically 29%
for herbicide tolerance, 24% for insect resistance, 20% for
product quality, 10% for viral resistance, 5% for agronomic
properties, 5% for fungal resistance, and 7% for other prop-
erties.355 Half of the world’s soybeans and one-third of its
corn came from plants genetically engineered for herbicide
or insect resistance.356 Other field trials for corn involve a
lower requirement for fertilizer and improved starch qual-
ity.357 Corn with B. thuringiensis genes can be eaten in
France, but not grown there.358 There is concern that resis-
tance developed to the antibiotics, such as ampicillin, used
as a genetic markers in 95% of transgenic crops might jump
to bacteria and make the antibiotics worthless in
medicine.359 Norway has banned all crops having antibi-
otic-resistance marker genes. It is now possible to produce
transgenic corn without the ampicillin marker. Transgenic
flax can be grown in herbicide-contaminated soil that
would otherwise prevent crop rotation.360
Plants may be able to serve as bioreactors for biophar-
maceuticals.361 -Linolenic acid has been made in tobacco
and Arabidopsis by inserting a gene coding for a -6-de-
Chapter 9
saturase.362 Human hemoglobin has been produced in a ge-
netically engineered tobacco plant.363 Therapeutic proteins
have been made in duckweed.364 If recombinant antibodies
can be produced in the seeds of plants, large-scale produc-
tion could be achieved at low cost. The product might be
stored in the seeds instead of in the refrigerator. At present
they are produced in microbial or mammalian cell cultures.
An effective edible vaccine for an E. coli strain that causes
diarrhea has been made in potatoes.365 Some human pro-
teins have been produced in the milk of transgenic cattle,
pigs, mice, goats, and rabbits.366 Human antithrombin III
and spider silk have both been produced in the milk of
transgenic goats.367 Human prolactin has been produced in
the milk of mice at 30–50 times the levels achievable in cell
culture.368 Human growth hormone has been produced in
the bladders of transgenic mice.369 Although the concen-
tration in the urine is low, the purification is simplified, be-
cause urine contains little protein and lipid. In contrast to
making it in milk, both sexes of the animals can be used
throughout their lives. Further work is needed on the use of
larger transgenic animals. Transgenic chickens are desired
for better disease resistance, altered sex ratio, and for pro-
duction of immunoglobulins in the eggs.370
There are some other risks in using agricultural biotech-
nology.371 Gene transfer might occur from genetically en-
gineered microorganisms to others in the environment.372
Genetically modified Pseudomonas fluorescens on wheat
was found up to 2 m away. The next year it was on newly
sown wheat plants and on nearby weeds.373 In sugar beets,
there was no transfer of marker genes to indigenous mi-
croorganisms. Yet, it is well known that bacteria can ex-
change genes on occasion. If corn, cotton, potato, and soy-
bean plants that incorporate B. thuringiensis genes for
insect resistance, hybridize with wild plants of the same or
related species, the resulting wild plant may be resistant to
herbivores that normally keep it in check. The result could
be a superweed. To envision the effect of a superweed, one
need only to think of some of the highly invasive noxious
weeds that have been brought to one country from another.
In the eastern United States, weeds such as Alliaria offici-
nalis, Rosa multiflora, Lonicera japonica, Celastrus orbic-
ulatus, Lythrum salicaria, and Pueraria lobata are threat-
ening native plant communities. The insect toxin now
transferred to the wild relative could kill off natural polli-
nators for the crop or other beneficial insects.374 Corn
pollen containing the B. thuringiensis toxin gene trans-
ferred to milkweed plants killed nearly half of the monarch
butterfly caterpillars that fed on them.375 Herbicide-resis-
tant crops may lead to additional use of herbicides with re-
sultant contamination of surface and groundwater. Addi-
tional soil erosion may occur compared with a field with a
surface cover crop under the main crop. There has already
Biocatalysis and Biodiversity
been a case of gene transfer from a crop of the mustard
family to a wild relative. The use of B. thuringiensis spray
on a regular calendar basis led to insect resistance in
Hawaii. Not everyone is satisfied with proposals to avoid
resistance by planting some nontransgenic plants in nearby
refugia.376 Labeling of transgenic crops has been suggested
to protect consumers who may be allergenic to the foreign
proteins present.377 A soybean that incorporated a gene
from Brazil nuts was not put on the market when testing
showed that people allergic to Brazil nuts were also sensi-
tive to the new soybean. The Ecological Society of Amer-
ica advises the use of caution in the introduction of trans-
genic organisms into the field. (For more on the
alternatives to traditional agriculture, see Chap. 11.)
II. BIODIVERSITY
A. The Value of Biodiversity
The discussion of biocatalysis has focused primarily on the
chemistry of microorganisms. The advantages of preserv-
ing as many different ones in as many different habitats as
possible should be apparent.378 The traditional search for
new types of activity has involved screening soil samples
from many different places. This implies the need to pre-
serve the varied places that the soils came from. Although
not as popular with persons who donate money for conser-
vation purposes as animals with fur or feathers, they are
just as important. The range of applications is extended
now that is possible to take the genes from one organism
and put them into another one.
Natives plants and animals are sources of new foods,
drugs, and other uses.379 They have also provided ideas for
new chemistry that would not have been thought of other-
wise. Roughly 80% of the top 50 prescription drugs used
today are of natural origin, or derivatives of them, or based
on leads from them.380 The ability to return to the wild for
new genetic material to breed into crops has saved a num-
ber of them. The classic case is the Irish potato famine of
the 19th century when a blight struck the potato crop. One
million people died and another 1 million emigrated out of
a total population of 6 million. In 1969–1970; 85% of the
hybrid corn was derived from a strain with a male sterility
trait. A crisis developed when a Southern corn blight at-
tacked the hybrid corn. Regular corn was not susceptible to
the blight.381 The disease resistance of a wild rice in India’s
forests saved much of Asia’s rice from a pandemic
blight.382 In California a uniform rootstock for grapes has
been threatened by a virulent disease, so that the rootstocks
are now being replaced by genetically varied ones.383 A
small wild patch of perennial corn in Mexico offers the
267
possibility of changing the corn crop from annual to peren-
nial, with savings in planting and soil erosion costs. An
everblooming strawberry found in Utah offers the possibil-
ity of strawberries at any time of the warmer part of the
year. Pinus radiata, originally found only in a small part of
California is now an important timber tree in many parts of
the world. The thousands of plants and animals used as
food in the past need to be reexamined for foods to supple-
ment the few dozen species that provide the bulk of the
world’s food today. Some may prove to be more nutritious
and more suitable for sustainable agriculture.
Many plants and animals have evolved chemical de-
fense systems to keep from being eaten or crowded out by
other plants.384 One way to look for new drug leads is to
test those plants and animals in the fields, forests,385 and
the seas,386 that are conspicuous and look like they could be
eaten easily. Another is to see what is used in tribal and
herbal medicine.387 Although some of these are surrounded
by myth and superstition, others have proved to be valuable
leads to new drugs. (The dangers of taking herbal supple-
ments before they have been thoroughly tested for safety
and efficacy were described in Chap. 1.) The hit rate for
drugs from plants is 1 in 125, whereas it is 1 in 10,000 for
chemically synthesized compounds.388 As a drug, a com-
pound does not necessarily have to be used for the same
purpose that it is in the wild. Botulism toxin can be used in
small amounts as a muscle relaxant.389 Curare, an Amazo-
nian Indian arrow poison, is useful as a skeletal muscle re-
laxant.390 The protein contortrostatin, found in the venom
of the copperhead snake, is able to reduce the rate of
growth of tumors by 90%.391 The deadly venom of the fish-
eating snail, Conus magus, contains a 25-amino acid
polypeptide that is a pain killer.392 Many compounds from
plants and animals are being screened against diseases for
which adequate drugs are not yet known, such as AIDS,
cancer, and Alzheimer’s disease.
Some of the more important substances found by
screening of natural products will be described in the fol-
lowing. Their chemical structures are given in Fig. 9.2. Be-
fore the discovery of colchicine, seven-membered rings of
carbon atoms were thought to be rare. It contains two fused
seven-membered rings. This discovery sparked the synthe-
sis of many more. Before the discovery that reserpine, from
the Indian vine Rauwolfia serpentina, could affect the
brain, chemical treatment of mental illness was not thought
to be possible. Today, many antidepressants are used.
Artemisinin from Artemisia annua (which is used in Chi-
nese herbal medicine) is effective against malaria that is re-
sistant to the usual drug chloroquine.393 It introduced the
idea that transannular peroxides can be effective drugs.
Simpler analogues also work.394 Hervelines from the bark
of Hernandia voyronii (used in herbal practice in Mada-
268 Chapter 9

Figure 9.2
Biocatalysis and Biodiversity
Figure 9.2 (Continued)
gascar) are also effective against drug-resistant malaria.395
The tree resists water well and has been used in dugout ca-
noes and coffins so much that it is now among the most en-
dangered species in the country. For it to be used as a
source of the drug commercially, the tree would have to be
farmed or the drug produced in tissue culture. Notice that
its structure has no relation to that of artemisinin.
Enediynes were not anticipated to be drugs, but calicheam-
icin, dynemicin, and others, are effective against cancer.396
This has spawned a great deal of activity in the synthesis of
enediynes and in studies of the their cyclization to aromatic
structures.397
Azadirachtin from Azadirachta indica (the neem tree) is
a potent insect antifeedant398 that promises to replace
harmful insecticides.399 Polygodial (from Polygonum hy-
dropiper) is another insect antifeedant.400 Before it can be
used widely, a way will have to be found to stabilize it
against environmental degradation. Balanol from fungi is a
potent inhibitor of protein kinase C enzymes and may lead
to new drugs for diseases involving these.401 The triterpene
betulinic acid, which is derived from the bark of the white
birch tree, is active against tumors.402 Cycloartenol triter-
penes from Cimicifuga foetida (used in traditional Chinese
medicines) are anti-inflammatory and analgesic agents.403
Bryostatin from a marine bryozoan is an anticancer
agent.404 Efforts are being made to farm the bryozoan to
produce the drug. Camptothecin is a natural quinoline
derivative that is used to treat ovarian cancer.405 Compactin
269
9.48
is effective in lowering cholesterol levels in the blood.406
Discodermolides are marine natural products that exhibit
immunosuppresive activity.407
Epibatidine (9.48) is a potent analgesic from the
Ecuadorian poison frog Epipedobates tricolor.408 Al-
though the compound itself is too toxic to use as a drug, an
analogue developed by Abbott Laboratories (9.49) is less
toxic, nonaddictive, and as effective as morphine.409
Epothilones A and B are promising anticancer agents
that bind to microtubules in the cell in the same way that
paclitaxel (Taxol) does and are more potent.410 Paclitaxel
was obtained first from the bark of the Pacific yew (Taxus
brevifolia).411 Widespread extraction of the compound
from this source could have wiped out the species. Fortu-
nately, it can now be extracted from the needles of more
common yews or produced in tissue culture. (See Sec II.C
on tissue culture.) Forskolin is a diterpene, from the roots
of Coleus forskohlii, that lowers blood pressure.412 Him-
bacine, from an Australian pine tree, offers a potential
treatment for Alzheimer’s disease.413 Combretastatin, from
the bark of the African bush willow, Combretum caffrum,
cuts the flow of blood to tumors, causing 95% of the can-
cer cells to die in 24 h, but does not harm healthy blood
vessels.414
Important drugs have been derived from two plants
common in the woodlands of the eastern United States.
One is etoposide (an anticancer drug) based on the
podophyllotoxin found in Podophyllum peltatum.415 The
second is sanguinarine (from Sanguinaria canadensis),
which is used for treatment of periodontal disease. A com-
mon fence lizard of the western United States, Sceloporus
occidentalis, has something in the blood that kills the bac-
teria responsible for Lyme disease.416
9.49
270 Chapter 9

Figure 9.2 (Continued)

Biocatalysis and Biodiversity
Figure 9.2 (Continued)
Some of the organisms from which the interesting drugs
have been obtained are of very limited distribution. Ra-
pamycin is produced by Streptomyces hydroscopicus,
which is endemic (grows nowhere else) to Easter Island in
the Pacific Ocean.417 The oil from Dicerandra frutescens,
a mint that grows only on a few hundred acres of Florida
scrub, is a natural insecticide.418 Curacin A, with potential
use in cancer therapy, was extracted from the blue-green
alga, Lyngbya majuscula, growing in the ocean on the
western side of Curacao.419 The same alga also contained
antillatoxin, which was toxic to fish, and barbamide, which
was toxic to snails. The same species growing at the north-
ern tip of the island produced little curacin A, but produced
kalkitoxin, a fish poison not found in the alga at the first
site. This shows the importance of preserving subspecies
and races as well as species of organisms.
B. Conservation of Natural Biodiversity
Man’s use of the land has brought many changes that have
resulted in an increased rate of extinction of species.420 The
greatest threat is from habitat destruction, followed in de-
scending order, by competition with alien species, pollu-
tion, overexploitation, and disease.421 One-fifth of all
271
freshwater fish are extinct, threatened or endangered.422
Physical alterations of rivers, contamination with sediment,
waste, or exotic species, in the United States have put 67%
of mussels, 64% of crayfish, 36% of fish, and 35% of am-
phibians in jeopardy or made them extinct. The introduc-
tion of the Nile perch to Lake Victoria in Africa has caused
the extinction or near extinction of many fishes. One-fourth
of the mammals in the world are at risk for extinction: 46%
of monkeys and apes; 36% of shrews and moles; 33% of
pigs, antelopes, and cattle; 11% of birds; 25% of amphib-
ians; and 34% of fishes.423 There is a worldwide decline in
amphibian populations for reasons that are just being iden-
tified. These may include fungal disease, parasitic worms,
increases in ultraviolet light, and so on.424 Of the species in
the United States in 1900, 1.5% are now extinct (8.6% for
freshwater mussels).425
The World Conservation Union reports that 34,000
plant species out of 270,000 are threatened.426 This in-
cludes one-third of all lily, palm, and Dipterocarpacae
species. Forests once covered 40% of the land on earth.
This has now been reduced by one-third.427 Tropical
forests have been reduced by 50% in the last 50 years, half
of this being due to slash and burn agriculture.428 More
than 2000 species of birds (about 15% of the world’s total)
272
Figure 9.2 (Continued)
have been lost in Polynesia since humans colonized the is-
lands.429 Losses have been highest in areas of high en-
demism. Some of this has been due to introduced animals,
such as predatory snails, the brown tree snake on Guam,
and the mongoose on Hawaii. Since 1778, Hawaii has lost
18 species of birds and 84 of the 980 species of plants. An-
other 133 of the species have populations of under 100
plants. A big problem has been the introduction of grazing
animals (i.e., goats and pigs) into an ecosystem that
evolved without grazing animals. Introduction of highly in-
vasive animals and weeds from other continents has led to
a loss of biodiversity.430 About 43% of the earth’s surface
has a reduced capacity to supply benefits to humankind
owing to overgrazing, deforestation, and other such condi-
tions.431 Acid rain has damaged the forests of Scandinavia
and the northeastern United States. Nitrogen from acid rain
has caused a reduction in biodiversity in grasslands, as na-
tive grasses have been replaced with weed grasses.432
Global warming may require a northern migration of
Chapter 9
species that cannot take place in many places because for-
est fragmentation has interspersed unsuitable habitat be-
tween forest fragments.433 Warming may also be too rapid
for migration to occur effectively.
There is a need for everyone to realize that biodiversity
is valuable.434 The goal is to save enough of each habitat in
each stage of succession so that there will always be
some.435 No-take reserves are being set up in an effort to re-
build overexploited fish stocks, as well as to protect terres-
trial species.436 They will work only if they include the ar-
eas of highest biodiversity and are large enough.437
Ecotourism is often suggested as a way to conserve biodi-
versity, but it must be managed carefully not to have a neg-
ative effect.438 Human population growth rates will have to
be slowed or even become negative to bring population
into balance with the natural resource base. (The chemistry
of family planning will be discussed in Chap. 16). Over-
consumption in the developed nations must be brought
down to a sustainable level. (Materials for a sustainable
Biocatalysis and Biodiversity 273

Figure 9.2 (Continued)

274
economy will be covered in Chap. 12; the chemistry of
longer wear in Chap. 13; energy from renewable sources in
Chap. 15; and the chemistry of recycling in Chap. 14.) The
sustainable use of forests should be possible without the
need to cut all of them.439 It is also important to see how
many degraded systems can be restored and to what ex-
tent.440 Many books in conservation biology and restora-
tion ecology are available for readers who wish to pursue
the subjects further.
C. Plant Cell and Tissue Culture
Any animals or plants that are found to contain valuable
drugs or other substances will have to grown in farms or in
cell culture to provide a reliable supply and to avoid over-
collection from the wild.441 In some cases where the
growth requirements are difficult to satisfy, it may be eas-
ier to transfer the proper genes to other organisms for
which cultural requirements are known. This assumes that
the substance or a compound of equivalent efficacy cannot
be made conveniently by chemical means.
Aquaculture is being used for organisms from the sea.
CalBioMarine Technologies is raising the bryozoan
Bugula neritina in closed culture to produce bryostatin 1. It
may be possible to raise a sessile marine organism on rafts
in bays, the way some oysters are raised in Japan.442 Plant
cell and tissue culture443 is a well-established technique
that can be useful for drugs, colorants, flavors, fragrances,
insect antifeedants, insecticides, and such. Ginseng, a fa-
vorite medicine in the Far East, is an example. The plant,
Panax ginseng, became scarce in the mountains of the east-
ern United States. The next step was to cultivate it on farms
in Wisconsin. The final step was to produce it in cell cul-
ture.444 One large run in Japan produced 1 ton of cells, the
same amount as 600 ha did in farms.
Plant cell and tissue culture has had some notable suc-
cesses in producing shikonin (a pigment), berberine, and
rosmarinic acid.445 In some other cases, the cultures have
not produced the same natural products in the same con-
centrations as in intact plants. There have also been occa-
sional problems of cell line instability. Higher plants grow
more slowly than microorganisms so that cultures may
need to be grown for a few weeks and kept sterile for this
time. These problems are being overcome gradually as
better knowledge of growth requirements, transport, and
compartmentalization of products, as well as biosynthetic
pathways accumulates.446 Sometimes, providing the
proper precursor can lead to increased yields.447 The
method has been used for chemical transformations, such
as ring closures. For commercial use, cultures that over-
produce relative to the wild plant are desired.
Chapter 9
Various methods have been used to increase yields.448
Varying the carbon/nitrogen ratio may help. It may be nec-
essary to use a two-stage culture with a growth phase fol-
lowed by a product-producing phase induced by a change
in the medium. Alternating sucrose-rich and nitrate-rich
media raised the yield of shikonin from Lithospermum ery-
throrhizon cell cultures.449 Because recovery of the prod-
uct may be 50–90% of the cost, it is desirable to select
strains that excrete the product into the medium while the
cells remain viable. If the product stays in the cells, they
must be broken up, and are lost, to recover the product. Ex-
cretion may be helped by pH changes, heat, electropora-
tion, and permeabilizers, such as dimethyl sulfoxide.450
Many of the compounds that are potentially useful as drugs
are produced by plants as defenses against attack by fungi,
insects, and larger herbivores. Treatment of cell cultures
with elicitors, such as fungal extracts or various microbial
polysaccharides, can often raise the level of the desired nat-
ural product.451 Continuous extraction of the desired prod-
uct can remove back inhibition and increase yields.452 San-
guinarine can be collected with silicone oils. It can also be
recovered from cultures of other cells with polymeric ad-
sorbents.453 Terpenes, which often are stored in oil glands
and tend to be volatilized from cell cultures, can be recov-
ered by extraction with a triglyceride of C8–C10 fatty
acids.454
Many secondary metabolites are produced in the roots
of plants. Treatment of roots separated from the plants with
Agrobacterium rhizogenes can cause them to grow rapidly
as “hairy roots”.455 This can cause increased production of
the desired compounds. Hairy root cultures of Catharan-
thus roseus made more vindoline than cell cultures.456
Such cultures of Papaver somniferum produced up to
2–10% dry weight of sanguinarine.457 Cultures of Sesa-
mum indicum made 50 times as much of the antimicrobial
compound 9.50 as the intact plant.458
A callus culture made by the transformation of Tri-
chosanthes kirilowii roots with Agrobacterium rhizogenes
9.50
Biocatalysis and Biodiversity
produced 1% by dry weight of a ribosome-inactivating pro-
tein compared with 0.01% in an ordinary dried root.459
Artemisinin has been produced by hairy root cultures of
Artemisia annua.460
By using the various techniques outlined in the forego-
ing, overproduction of various compounds has been
achieved. A few examples will be given. A cell suspension
culture of Rauwolfia serpentina produced 12 times as much
raucaffricine as intact plants.461 A callus culture of Dauca
carota produced up to 15% by dry weight of an antho-
cyanin.462 Cultured cells of Aralia cordata contained 13%
by dry weight of an anthocyanin after 3-weeks growth.463
Anthocyanins are being studied as natural food colors.
Coptis japonica cells can make up to 10% berberine.464
Callus of Eremophila spp. can accumulate up to 20% of dry
weight of verbascoside.465 When Mentha spicata plantlets
from shoot tip culture are grown on the right medium, the
yield of monoterpenes can be higher than in the intact
plant.466 Considerable effort has been focused on a way to
prepare paclitaxel (Taxol) by cell culture.467 Most of the
compound is excreted to the medium. The best yields have
been obtained by the use of methyl jasmonate as an elici-
tor.468 Taxus media cells grown in suspension for 2 weeks
produced 0.606% paclitaxel, compared with the usual
0.007% in dry yew bark. Methyl jasmonate (9.51) is pro-
duced by plants in response to wounding. It causes the syn-
thesis of protease inhibitors.
Plant cell and tissue culture methods can be used for the
mass propagation of plants. Cells (often from the growing
tip) can be grown in a medium containing one hormone to
form a callus or a suspension.
Changing to another hormone causes plantlets to
form.469 Each cell contains all the genetic information
needed to form a whole plant. The process is called somatic
embryogenesis. Much effort has been expended to extend
the method to a large variety of families of plants, primar-
ily those of economic interest. Practically all the house
plants sold in the United States are propagated this way in
Florida. The method is simple enough so that it can be per-
formed in the basement of one’s home if one knows how.
In Vietnam homes, it has been used to propagate potatoes,
coffee, sugarcane, and orchids.470 It is very useful with
9.51
275
bamboo, which does not bloom very often, as well as with
trees that may take many years to reach flowering size. The
goal is to make it easier to propagate plants this way than
to collect them in the wild and thus prevent overcollecting.
The method can also be used to propagate rare plants for
reintroduction into their former ranges in the wild. To
maintain genetic diversity, more than one source of plant
material should be used.
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culture and Forestry, vol 20—High Technology and
Micropropagation. Springer, Berlin, 1992. (q) JP Kut-
ney. Pure Appl Chem 1997; 69:431. (r) T–J Fu.
Chemtech 1998; 28(1):40. (s) AH Shulman. Trends
Biotechnol 1998; 16:1. (t) S Cuppett. Int News Fats
Oils Relat Mater 1998; 9:588. (u) H Dornenburg, D
Knorr. Food Technol 1997; 51(11):47 and following
papers, pp 56–72.
444. (a) Y–H Zhang, J–J Zhong, J–T Yu. Biotechnol Prog,
1996; 12:567. (b) A Scheidegger. Trends Biotechnol
1990; 8:197. (c) O Sticher. Chemtech 1998; 28(4):26.
(d) Y–H Zhang, J–J Zhong. Enzyme Microb Technol
1997; 21:59.
445. TM Kutchan, A Bock, H Dittrich. Phytochemistry 1994;
35:353.
Chapter 9
446. JP Kutney. Acc Chem Res 1993; 26:559; Pure Appl Chem
1999; 71:1025.
447. JP Kutney. Pure Appl Chem 1996; 68:2073; 1994; 66:2243.
448. (a) RM Buitelaar, J Tramper. J Biotechnol 1992; 23:111.
(b) R Tom, B Jardin, C Chavarie, J Archambault. J
Biotechnol 1991; 21:1. (c) R Tom, B Jardin, C
Chavarie, D Rho, J Archambault. J Biotechnol 1991;
21:21. (d) B Jardin, R Tom, C Chavarie, D Rho, J Ar-
chambault. J Biotechnol 1991; 21:43. (e) R Ballica,
DDY Ryu, CI Kado. Biotechnol Bioeng 1993; 41:1075.
(f) DI Kim, H Pedersen, C–K Chin. J Biotechnol 1991;
21:201. (g) AK Lipsky. J Biotechnol 1992; 26:83. (h) H
Dornenburg, D Knorr. Enzyme Microb Technol 1995;
17:674.
449. V Srinivasan, DDY Ryu. Biotechnol Bioeng 1993; 42:793.
450. C–H Park, BC Martinez. Biotechnol Bioeng 1992; 40:459.
451. (a) IM Whitehead, DR Threlfall. J Biotechnol 1992; 26:63.
(b) NP Malpathak, SB David. Biotechnol Lett 1992;
14:965. (c) M Tani, K Takeda, K Yazaki, M Tabata.
Phytochemistry 1993; 34:1285. (d) H Dornenburg, D
Knorr. J Agric Food Chem 1994; 42:1048. (e) SK Ri-
jhwani, JV Shanks. Biotechnol Prog 1998; 14:442.
452. P Brodelius, H Pedersen. Trends Biotechnol 1993; 11:30.
453. RD Williams, N Chauret, C Bedard, J Archambault.
Biotechnol Bioeng 1992; 40:971.
454. AJ Parr. J Biotechnol 1989; 10:1.
455. (a) HE Flores. Chem Ind (Lond) 1992:374. (b) SA McK-
elvey, JA Gehrig, KA Hollar, WR Curtis. Biotechnol
Prog 1993; 9:317. (c) PM Doran, ed. Hairy Roots—
Culture and Applications. Harwood Academic, Ams-
terdam, 1997.
456. (a) R Bhadra, S Vani, JV Shanks. Biotechnol Bioeng 1993;
41:581. (b) SK Rijhwani, JV Shanks. Biotechnol Prog
1998; 14:442.
457. RD Williams, BE Ellis. Phytochemistry 1993; 32:719.
458. T Ogasawara, K Chiba, M Tada. Phytochemistry 1993;
33:1095.
459. JE Thorup, KA McDonald, AP Jackman, N Bhatia, AM
Dandekar. Biotechnol Prog 1994; 10:345.
460. CZ Liu, YC Wang, F Ouyang, HC Ye, GF Li. Biotechnol
Lett 1998; 20:265.
461. DH Schubel, CM Ruyter, J Stockiat. Phytochemistry 1989;
28:491.
462. L Rajendran, GA Ravishankar, LV Venkataraman, KR
Prathiba. Biotechnol Lett 1992; 14:707.
463. K Sakamoto, K Iida, K Sawamura, K Hajiro, Y Asada, T
Yoshikawa, T Furuya. Phytochemistry 1993; 33:357.
464. K Matsubara, S Kitani, T Yoshioka, T Morimoto, Y Fujita,
Y Yamada. J Chem Technol Biotechnol 1989; 46:61.
465. B Dell, CL Elsegood, EL Ghisalberta. Phytochemistry
1989; 28:1871.
466. T Hirata, S Murakami, K Ogihara, T Suga. Phytochemistry
1990; 29:493.
467. (a) M Seki, S Furusaki. Chemtech 1996; 26(3):41. (b) LJ
Pestchanker, SC Roberts, ML Shuler. Enzyme Microb
Technol 1996; 19:256. (c) N Mirjalili, JC Linden.
Biotechnol Prog 1996; 12:110.
Biocatalysis and Biodiversity
468. (a) Y Yukimune, H Tabata, Y Higashi, Y Hara. Nat
Biotechnol 1996; 14:1129. (b) J Pezzuto. Nat Biotech-
nol 1996; 14:1083.
469. PD Denchev, AI Kuklin, AH Scragg. J Biotechnol 1992;
26:99.
470. M Timm. Biotechnology 1989; 7:118.
471. G Zhong, RA Lerner, CF Barbas III. Angew Chem Int Ed
Engl 1999; 38:3738.
472. Anon. Chem Ind (Lond) 1999; 689.
RECOMMENDED READING
1. JW Frost, J Lievense. New J Chem 1994; 18:341; or JW
Frost, KM Draths. Chem Brit 1995; 31:206.
2. AD Kinghorn, MF Balandrin, eds. Human Medicinal Agents
from Plants. ACS Symp 534, Washington, DC, 1993, pp
2–10.
3. F Flam. Science 1994; 266:1324.
4. MWW Adams, RM Kelly. Chem Eng News 1995; Dec
18:32.
5. AJ Kirby. Angew Chem Int Ed Engl 1996; 35:720–722.
6. J Lalonde. Chem Eng 1997; 104(9):108.
7. AL Paiva, FX Malcata. J Mol Catal B Enzym 1997;
3:99–106.
EXERCISES
1. Visit a microbiology laboratory near you to see how
fermentation is done.
2. Check the library for books on fermentation that
were written in 1910–1930 to see what compounds
289
were made by the method then that are made from
petroleum or natural gas today. What modern tech-
niques would you use to improve the processes to
make them competitive today?
3. Pick a present-day process for a large volume
chemical that is made by a process that is energy-
intensive or involves the use of toxic reagents or
catalysts. How would you go about finding an or-
ganism that would make the same chemical from
renewable resources? You may need to use a sim-
ple chemical step in addition to the biocatalytic
ones.
4. Are there any food-processing plants in your area
that are having waste disposal problems? If so, see
if you can devise a biocatalytic system to make
something useful and saleable from the wastes.
5. Check with your state Natural Heritage Program (or
an equivalent program if you live in a country other
than the United States) to see what percentage of
the native flora and fauna are extinct, endangered,
or threatened. See if you can find out why these
populations are in trouble?
6. Check with your department of agriculture to see
what exotic plants and animals are in your area and
what threats they pose to the native flora and fauna.
Then go into the field to verify this.
7. Pick a reduction by baker’s yeast in a recent journal
or in Organic Syntheses. Using this procedure try
reducing a different compound by this method.
10
Stereochemistry
I. THE IMPORTANCE OF OPTICAL
ISOMERS
Most organic molecules in living organisms contain
asymmetrical centers (i.e., they are chiral). (The terminol-
ogy of stereochemistry has been reviewed by Moss.1) For
example, amino acids that are incorporated into proteins
are L and sugars in carbohydrates are D. It is understand-
able that the three-dimensional structures of the receptors
in proteins for small molecules will favor only one optical
isomer (i.e., the one that fits sterically, hydrogen bonds
properly, and so on). Most compounds made for use by
plants and animals will have to be single optical isomers.
10.1
291
These include agricultural chemicals, drugs, flavors, food
additives, fragrances, and such. This is especially impor-
tant with drugs,2 for which the unwanted isomer may pro-
duce toxic side effects.
There are several possibilities: (a) The unwanted isomer
may be inert, in which case its synthesis is a waste, for it
must be discarded or recycled, if this is possible. (b) The
unwanted isomer is useful for another entirely different
purpose. (c) The unwanted isomer can ruin the effects of
the desired one and may prove to be toxic.3 (d) The isomers
may racemize in the body so that the racemate may be used.
Sheldon has listed some examples (10.1) that illustrate
these cases.4
292
The reader will appreciate the difference in the flavors
of the two terpene isomers. Aspartame is the popular artifi-
cial sweetener found in many soft drinks and other foods.
Dramatic differences can also be found in the isomers of
drugs (10.2).
Some drugs may not need to be single isomers because
they racemize in the body. The analgesic ibuprofen (10.3)
is an example. Even so, Merck planned to market the S-iso-
mer as faster-acting (12 min versus 30 min for the racemic
drug).2d (The isomerization presumably involves removal
of a proton from the carbon atom  to the carboxylic acid.)
10.2
Chapter 10
Whether this is applicable to other drugs that isomerize in
the body depends on the rate of isomerization and the rate
at which the desired effect is wanted.
Optical isomers can also have different effects on plants
(10.4)
II. THE CHIRAL POOL
The desired optical isomer can sometimes be produced as a
natural product. The caraway and spearmint flavors men-
Stereochemistry
10.3
10.4
tioned earlier (see 10.1) are extracted from crop plants.
Other single isomers can be produced by enzymatic reac-
tions, as described in Chap. 9. Thus, the L-aspartic acid and
L-phenylalanine needed to make aspartame could be ob-
tained in this way. In some instances, chemical synthesis
may be better. In others, it may be the only way to obtain
the compounds.
10.5
293
Almost all the syntheses require a natural product or a
derivative of one. These are drawn from a chiral pool of al-
kaloids, amino acids, hydroxy acids, sugars, terpenes, and
others. Typical alkaloids include ephedrine, cinchonidine,
quinidine, and sparteine (10.5).
Typical L-amino acids are glutamic acid, lysine, pheny-
lalanine, and proline (10.6)
294 Chapter 10

10.6

There are many other -amino acids. These have been

selected to show typical diversity, one with an extra car-
boxylic acid group, one with an extra amino group, an aro-
matic one, and one with a heterocyclic ring. Derivatives of
-amino acids, such as the amino alcohols obtained by re-
duction of the acids or their esters, are also used.
L--Hydroxyacids such as those in 10.7 can be used.
5

Many derivatives of tartaric acid are used, including es-

ters and the diols resulting from the addition of Grignard
reagents to their ketals.
D-Sugars such as glucose, lactose, and sucrose (10.8) are 10.9
also used.6
Derivatives obtained by oxidation, reduction, and other
means are also used (10.9).

10.7

10.8
Stereochemistry
10.10
Terpenes used include 3-carene, camphor, limonene,
menthol, and - and -pinenes, as well as their derivatives
(10.10).
Addition of borane to -pinene produces a useful chiral,
reducing agent. 10-Camphorsulfonic acid is a useful re-
solving agent for amines.
Chiral chemistry is a very active field covered by nu-
merous books7 and reviews.8 The treatment here will em-
phasize the themes of earlier chapters.
1. Minimize waste, especially toxic wastes. Pick pro-
cesses that do not discard the 50% of unwanted iso-
mer. Avoid waste salts.
2. Avoid solvents, especially toxic ones, when
possible.
3. Avoid toxic reagents and harsh or energy-intensive
conditions.
4. Keep the number of steps low. Avoid systems that
require putting on a chiral auxiliary, running the de-
sired reaction, then removing the auxiliary.
5. Provide for the simple recovery and recycle of chi-
ral ligands.
6. Find conditions that give close to quantitative
yields and enantioselectivity to avoid further pro-
cessing that may reduce yields. For example, losses
can occur when crystallization is necessary to in-
crease the enantiomeric excess (ee).
7. Find conditions that produce the desired compound
in a reasonable time and with a simple workup.
295
III. RESOLUTION OF RACEMIC MIXTURES
In a few cases it is possible to crystallize the desired opti-
cal isomer by seeding a supersaturated solution of the race-
mate with the desired isomer. This has been used with a
sulfide ester alcohol intermediate in the synthesis of the
drug diltiazem (10.11).2d
Repeated crystallization of the racemate of the com-
pound in 10.12 led to preferential enrichment of the enan-
tiomers (up to as much as 100% ee) in the mother liquor.9
High-intensity circularly polarized light has been used
to destroy the unwanted isomer of racemic tartaric acid.10
L-Tartaric acid was obtained in only 11% ee. Considerable
development work will be needed to raise this to a useful
level. A disadvantage of the method is that it wastes 50%
of the material.
The molecular recognition of chiral guests by enan-
tiomerically pure hosts to form inclusion can be used to
separate racemates11 (as mentioned in Chap. 7). Thus, 1,1-
bi(2-naphthol) (BINOL; 10.13) has been used to separate a
variety of nitrogen, phosphorus, and sulfur compounds, in-
cluding amine oxides and sulfoxides. The procedure can be
as simple as mixing the guest with the host, then distilling
off the unwanted isomer. The desired isomer is then ob-
tained by stronger heating under vacuum. A diol derived
from tartaric acid has been used to obtain alcohols and
epoxides with more than 97% ee (10.13).
The mixture to be resolved is stirred with a suspension
of the host diol, followed by filtration of the inclusion com-
296
10.11
10.12
10.13
pound. The guest is released by heating under vacuum. The
host can be used over again. The method is described as
simple, inexpensive, and environmentally safe. There is the
disadvantage of having to locate a suitable host, especially
for larger and more complicated molecules. BINOL can be
resolved by formation of a 1:1 inclusion compound (10.14)
with a quaternary ammonium salt derived from the amino
acid, leucine.12 The quaternary ammonium salt can be re-
covered for reuse. 2-Alkylcyclohexanones have been re-
solved in 100% yield (74–94% ee) by formation of an in-
10.14
Chapter 10
clusion compound with the cyclohexanone ketal analogue
of the foregoing ketaldiol.13
A methylated -cyclodextrin (10.15) has been used as a
host to resolve a ketal in water.14
The inclusion compound of the R isomer precipitates
from water in 77% yield. The yield is higher than 50% be-
cause there is some equilibration of the isomers in water.
To prevent isomerization in storage, it is stored as the
10.15
Stereochemistry
host–guest complex. The compound is a sex pheromone of
the olive fly.
As mentioned in Chap. 7, molecular imprinting of poly-
mers15 can also be used to prepare hosts for the removal of
the desired optical isomer from racemates. Foam flotation
with imprinted polymers has been used in chiral separa-
tions.16 Flotation is often used to separate minerals from
their ores. The polymers can be reused repeatedly. This
may turn out to be the lowest-cost method of resolution.
Diastereoisomeric resolution is a standard method that
is still used in the preparation of 65% of single-isomer
drugs.2d This involves reacting the racemic mixture with an
optically active resolving agent to form a mixture of di-
astereoisomers that can be separated by crystallization.
Lactic, mandelic, or camphorsulfonic acid might be used
with an amine. Chiral crown ethers can also be used with
amines.17 An optically active -methylbenzylamine,
ephredrine, or another alkaloid might be used with a car-
boxylic acid. The use of families of structurally related re-
solving agents has led to more rapid separations.18 DSM is
using this method on a scale of hundreds of kilograms. An
example is the use of a single enantiomer of tartaric acid,
acylated with benzoic, p-toluic, and p-anisic acids, to re-
solve O-chloro--phenethylamine. The use of expensive
alkaloids can be avoided in the resolution of -hydroxy-
and -alkoxyacids through the use of calcium O,O-diben-
zoyltartrate.19
An alcohol could be converted to an ester, which could
be hydrolyzed back to the alcohol after the separation, pro-
viding conditions that would not favor racemization during
the hydrolysis were selected. The problems with this
method are that the maximum yield will be less than 50%
if there are any losses in crystallization, and waste salts will
be formed when the desired isomer is liberated from its salt
or ester. The resolving agent, which may be expensive,
must be recovered in high yield for recycling to the next
run.
Chiral columns are used routinely for the analytical sep-
aration of optical isomers.20 Typical columns use triben-
zoates, or tris(phenyl carbamates), of cellulose or amylose
as well as cyclodextrins. Flash chiral chromatography has
10.16
297
also been performed on a cellulose carbamate on silica.21
Preparative-scale chiral chromatography is being adapted
to larger amounts that are sufficient for the preparation of
some drugs: 10,000 kg/yr of (R)-3-chloro-1-phenyl-
propanol is separated this way.2d Simulated moving-bed
chromatography, in which a series of columns are linked in
a cycle with the solution being pumped around repeatedly,
and the head and tail of the band taken off in each cycle, is
used. This uses less solvent, but more packing, than the
usual column chromatography. For some drugs that are not
needed in large amounts, this can be the cheapest and
fastest way to proceed.142
Chiral membranes have also been used to separate iso-
mers. A cellulose tris(3,5-dimethylphenyl carbamate) has
been used to separate an amino alcohol -blocker, al-
though the S isomer was obtained in only 55% ee and the
R isomer in 23% ee.22 On the other hand, a chiral mem-
brane of a poly(L-glutamate) derivative completely re-
solved racemic tryptophan.23 Apoenzymes (enzymes lack-
ing their usual cofactor) have been placed in the pores of
a membrane consisting of a gold film covered with
polypyrrole.24 In one of these, D-phenylalanine passed
through five times faster than the L-isomer. (For more de-
tail on membrane separations, see Chap. 7.) This method
holds considerable promise for catalytic membrane reac-
tors, especially if the unwanted isomer can be racemized
in situ.
Enzymes are often used in kinetic resolutions, when one
isomer reacts much faster than the other.25 This can be done
on an industrial scale. Zeneca uses a dehalogenase on
racemic 2-chloropropionic acid to obtain about 2000 ton/yr
of the L-isomer for use in making a herbicide.26 Enzymatic
resolutions may involve ring opening of epoxides,27 for-
mation or hydrolysis of esters and amides, reduction of car-
bonyl compounds, and so on. Lipases are often used for this
purpose.28 A typical example is reaction 10.16.29
Various factors affect the enantioselectivity in such hy-
drolyses. These include the concentration and the choice of
the organic solvent used.30 In another, pretreatment of the
lipase with 2-propanol raised the enantioselectivity 25-fold
to 93% ee.31 In an esterification of menthol, coating the
298
10.17
lipase with a surfactant raised the activity in isooctane 100-
fold.32 Entrapment of the lipase in a gel made by the
hydrolysis of a mixture of tetramethoxysilane and n-propy-
ltrimethoxysilane (10.17) improved the activity severalfold
and raised the enantioselectivity. The catalyst could be
reused many times, although there was a 15–20% loss of
activity in the first two or three cycles after which the ac-
tivity became constant.33
Microwave radiation increased the rate 1- to 14-fold and
the ee 3- to 9-fold (up to 92% ee for one isomer and 96% ee
for the other) in the lipase-catalyzed esterification of an al-
cohol with vinyl acetate.34 Ultrasound increased the rate 7-
to 83-fold. Directed evolution can occasionally be used to
improve the enantioselectivity of lipases. A lipase for the
hydrolysis of racemic p-nitrophenyl 2-methyldecanoate
that gave 2% ee was run through four generations of error-
prone polymerase chain reactions to raise the selectivity to
81% ee.35
Lipases have also been used to prepare enantiomerically
pure amines (10.18).36
10.18
Chapter 10
L-Methionine has been prepared from N-acetyl-D, L-me-
thionine by deacylation with an aminoacylase.37 The lipase
was supported on an ion-exchange resin. The reaction was
driven to completion by chromatographic ion-exchange re-
moval of the by-product acetic acid and unreacted sub-
strate, the racemic mixture being fed in pulses to the col-
umn. The cross-linked enzyme crystals marketed by Altus
Biologics are very useful in enzymatic resolutions, because
of their enhanced stability to heat and organic solvents and
because they can be reused many times. (For more detail on
enantiospecific reactions with enzymes, see Chap. 9.)
The problem with most of the foregoing methods is that
the maximum yield is 50%. The unwanted isomer is often
discarded as waste. In other instances, it is racemized38 by
acid, base, heat, a racemase,39 or other means, then recy-
cled to the process. Base works well with any carbonyl
compound that has a hydrogen atom on the -carbon atom.
A convenient way to racemize amines is to make a Schiff
base with benzaldehyde which then can isomerize by way
of the isomeric ketamine (10.19).
Stereochemistry 299

10.19

10.20

10.21

When resolution and racemization are carried out in the
same vessel at the same time, the process has been termed
deracemization or dynamic resolution.40 The maximum
yield then becomes 100%, with no need to recycle an un-
wanted isomer. Several examples will be given to illustrate
the scope of this approach.
The R,R isomer of -bromoamide (10.20) reacts faster
than the S,R isomer.41
Biocatalytic deracemization can be accomplished where
the racemizing agent is either biological or chemical.42
Two organisms have been used together to hydrolyze
styrene oxide. Aspergillus niger works only on the R iso-
mer with retention of configuration. Beauveria bassiana
uses only the S isomer with inversion. The result is that a
single product is formed (10.21).
Geotrichum candidum has been used to deracemize 1-
arylethanols (10.22).43
At least two enzymes are thought to be involved in a
process that must go through oxidation to the ketone, then
reduction to the alcohol. An alcalase, in the presence of
pyridoxal-5-phosphate as an isomerizing agent, has been
used to convert racemic amino acid esters to the L-enan-
tiomers with 90–98% ee in 87–95% yield.44
Silica has been used to promote hemithioacetal epimer-
ization by dissociation–recombination in an enzymatic es-
terification (10.23).45
A palladium salt has been used to isomerize an allylic
acetate during an enzymatic hydrolysis (10.24).46
An allylic alcohol isomerized during an enzymatic es-
terification (10.25).47
10.22
300 Chapter 10

10.23

10.24

Triethylamine has been used as a racemizing agent in
the hydrolysis of thioesters (10.26).48
Other dynamic resolutions involve in situ racemization
by reversible Michael reactions,49 retroaldol reactions,50
enolization of esters,51 and Ru(II)-catalyzed isomerization
of alcohols.52
These examples are a step in the right direction, but im-
provements are still needed. Some of the reactions take
place over days. The times might be shortened by using en-
zymes that are active at higher temperatures. When the en-
zymatic reactions are carried out in organic solvents, the
times might be shortened by using a surfactant or by using

10.25

10.26
Stereochemistry 301

cross-linked enzyme crystals (as described in Chap 9). The

use of immobilized enzymes and supported catalysts may
help in the workups and in the recycling for the next run.
There are still some by-products to be removed. Fre-
quently, there is still the need to prepare an ester in a sepa-
rate step before obtaining the desired acid or alcohol from
the resolution. Two of the foregoing examples are espe-
cially instructive. The resolution of racemic 1-arylalkanols
with Geotrichum candidum in water (see 10.22) gave up to
99% ee without the need to make any derivatives or use any
chemical reagents. The quantitative resolution of racemic
tryptophan by a poly(L-glutamate) membrane used no
derivatives and no chemical reagents. These suggest the
use of a deracemization catalyst, chemical or biological, in
conjunction with a chiral membrane in a continuous reac-
tor. The catalyst could be in solution or in the membrane.
This could be the quickest and least-expensive way to
make the alcohols, amines, carboxylic acids, and such,
needed for single-isomer drugs, flavors, agricultural chem-
icals, and the like. It would also produce the least waste.
Use of a membrane reactor in the continuous reduction of
an emulsion of 2-octanone to S-2-octanol (99.5% ee)
with a Candida parapsilosis reductase increased the
turnover number by ninefold, compared with a classic re-
actor.53 (For more on membrane separations, see Chap 7.)
Catalytic antibodies have been used to resolve aldols by
the retroaldol reaction to obtain 95–99% ee.54
Benzyl alcohols have been resolved in parallel kinetic
resolutions that use two reagents with selectivities for
opposite isomers to make carbonates in simultaneous
reactions (10.27).55
10.28
Some racemic compounds might be separated without
the need to make chemical derivatives. Chiral diols bond
selectively (SS-isomer favored over the RR-isomer by a
factor of 6 or 7) by hydrogen bonding to the amidine
(10.28).56
IV. ASYMMETRICAL SYNTHESIS
The best approach is to start with a natural optically active
compound and modify it by reactions that will not racem-
ize the product or intermediates. Unfortunately, this is pos-
sible in only a relatively few cases. Some of the problems
mentioned in the foregoing might be solved if one could
devise a catalytic asymmetrical synthesis for a desired
compound.57 Activity in this field is intense. The many
small companies in this field (plus some of their suppliers)
include the following:
Altus Biologics, Cambridge, Massachusetts: enzymes
for syntheses

10.27
302
Austin Chemical, Buffalo Grove, Illinois: chiral chro-
matography
Boehringer Mannheim, Mannheim, Germany: enzymes
for syntheses
Celgene, Warren, New Jersey58
Chemi, Milan, Italy
Chiragene, Warren, New Jersey
Chiral Technologies, Exton, Pennsylvania: chiral chro-
matography
ChiRex, Dudley, England
Chiroscience and ChiroTech, Cambridge, England59
Daiso, Osaka, Japan
Kaneka, Osaka, Japan
Oxford Asymmetry, Abingdon, England
SepraChem and Sepracor, Marlborough, Massa-
chusetts32
SynChem, Chicago, Illinois
Synthon, Lansing, Michigan: chiral reagents
Takasago, Rockleigh, New Jersey
Zeeland, Zeeland, Michigan
Ideally, the product would be made in 100% ee so that
no crystallization would be needed and no losses would oc-
cur. In practice, this seldom happens. To be useful com-
mercially, the enantiomeric excess should be over 90% so
that a minimal number of crystallizations will provide the
pure optical isomer. Many of the reactions reported in the
literature do not meet this standard. However, they may be
important mileposts on the way to high enantioselectivity.
Despite the successes of computational chemistry in many
areas, it is still not possible to model the transition states of
the reactions well enough to select catalysts that will pro-
vide high stereoselectivity. Most of the good catalysts are
found empirically and raised to high selectivity by system-
atic variation of the substituents. The application of combi-
natorial chemistry may help. Rather than finding a general
catalyst that gives high enantioselectivity and yields for a
whole class of compounds, it may well be necessary to tai-
lor the steric and electronic effects in each one to a specific
10.29
Chapter 10
substrate and set of conditions. Reasonable turnover rates
are also required for the catalysts. Some of the better meth-
ods of asymmetrical synthesis will be described in the fol-
lowing, together with their advantages and limitations.
Chiral auxiliaries are often used on a stoichiometric ba-
sis. They are often derived from natural amino acids and
the amino alcohols obtained by their reduction.60 A typical
alkylation reaction (10.29) carried out in this way is
shown.61 (Similar alkylations have been carried out using
polymeric analogues, the ee varying with the resin used (up
to 90% ee when Wang resin was used).62
The starting compound was also condensed with an
aldehyde in 82–84% yield with more than 98% ee. A cor-
responding amide from an --unsaturated acid underwent
the Diels–Alder reaction in 86–90% yield with more than
99% ee. The original amino alcohol was probably treated
with phosgene to close the oxazolidone ring.63 The less
toxic dimethyl carbonate might be a suitable replacement
for the phosgene. The use of another chiral auxiliary for
alkylation is shown in 10.30.64
Terpene derivatives are also used as chiral auxiliaries, as
in example 10.31.65
Although these syntheses give high enantioselectivity,
they do have associated problems. It is necessary to make
the chiral auxiliary in more than one step, to use it on a sto-
ichiometric basis, and to recover it at the end for recycling.
Some of the reagents may be toxic. Separating the chiral
auxiliary or its remnants from the product may complicate
the workup. Waste salts are produced in the process. The
process can be expensive.
Asymmetrical reduction of ketones to alcohols66 can be
done in a number of ways. Reductions with microorgan-
isms67 were described in Chap. 9. By choosing appropriate
microbes both R and S isomers were obtained. The inclu-
sion of dimethylsulfide in a reduction of -ketoesters with
Baker’s yeast raised the enantioselectivity from 94 to
98%.68
A stoichiometric amount of a chiral borane, such as di-
isopinocampheylchloroborane, which is made by addition
Stereochemistry 303

10.30

10.31

of borane to -pinene, can be used to achieve enantiomeric

excesses as high as 91–98%.69 Achiral boranes can be used
in stoichiometric amounts with a chiral catalyst (10.32).70
The catalyst was designed using a transition state model.
The ee was lower in methylene chloride than in toluene.
Other workers have used this type of catalyst in a poly-
meric form to simplify the workup (10.33).71
The dimethylsulfide adduct of borane was the reducing
agent, giving the alcohol in up to 89% ee in 95% conver-
sion in 20 min. The catalyst could be reused at least three
times. The reduction has also been carried out by transfer 10.33
hydrogenation using 2-propanol as the hydrogen donor and
ruthenium complexes as catalysts with enantiomeric ex-

10.32
304
10.34
cesses up to 98%.72 A variety of catalysts were used, two
of which are shown in 10.34.
Catalytic reductions produce far less waste or material
to be recycled than methods that use stoichiometric
amounts of reducing agents. They usually give higher vol-
ume yields and productivities than microbial reductions.73
-Ketoesters have been reduced with hydrogen using
a cinchona alkaloid-modified platinum catalyst to give
up to 95% ee.74 Methyl pyruvate was reduced to 98.8%
R-methyl lactate and 1.2% S-methyl lactate using
this method with a poly(vinyl pyrrolidone)–stabilized
catalyst.75
One of the most popular ligands is BINAP (2,2-
bis(diphenylphosphino)-1,1-binaphthyl)76 which can be
made from BINOL (1,1-bi-2-naphthol) through its ditri-
flate77 (10.35). (The synthesis of BINOL from 2-naphthol
by oxidation with air was given in Chap. 4. Resolution of
the BINOL can be accomplished with the inclusion com-
10.35
Chapter 10
pound described earlier in this chapter, or with N-benzyl-
cinchonidium chloride,78 or through a cyclic menthyl phos-
phite.79 A polymer-supported BINAP, available commer-
cially, can be recovered for reuse by filtration.80
A tetrakis (sodium sulfonate) from BINAP has been
used with a ruthenium catalyst in a thin film of ethylene
glycol on porous glass in the asymmetrical reduction of an
unsaturated carboxylic acid (10.36).81
The catalyst could be reused several times, an important
factor considering the high cost of ruthenium and the lig-
and. No ruthenium was lost by leaching. Even so, the ruthe-
nium would have to be recovered chemically after the use-
ful life of the catalyst. Chiral ruthenium catalysts can also
be used to reduce cyclic Schiff bases in 82 to more than
99% yield with 77–97% ee.82
Optimization of the phosphine ligands has led to high
enantioselectivity in the hydrogenation of -acetami-
doacrylic esters with rhodium catalysts and of -ketoesters
Stereochemistry
10.36
with ruthenium catalysts.83 Two of the diphosphine ligands
are shown in 10.37.
The diphosphine on the left was used with a rhodium
catalyst and hydrogen to reduce the dehydroamino acid
derivatives. The same reduction could also be carried out
with sugar-derived phosphinites, the product being ob-
tained in 97–99% ee.84 The diphosphine on the right, or
better its counterpart, in which isopropyl has replaced
methyl, was used with a ruthenium catalyst and hydrogen
or 2-propanol in the reductions of -ketoesters. 1-Acetyl-
naphthalene was reduced with a ruthenium catalyst using
the ligand on the left with 2-propanol (10.38) in more 99%
yield and 97% ee.
10.37
10.38
305
The top reaction (where R  phenyl, R  R  methyl)
has been run with a different diphosphine using a poly-
meric surfactant as the anion for rhodium to give 90–92%
ee.85 Optimization of the phosphine structure would prob-
ably raise this to the levels shown in 10.38. The polymeric
surfactant was derived from a copolymer of acrylamide
with maleic anhydride (10.39).
The catalyst could be filtered off and reused up to nine
times. This shows the advantages of supported catalysts in
simplifying workups and in the conservation of expensive
materials.
BINOL has also been used in many other catalysts for
asymmetrical synthesis. A ruthenium BINOL complex in a
306
10.39
10.40
poly(dimethylsiloxane) membrane was used to reduce
methyl acetoacetate with hydrogen to the corresponding al-
cohol ester with 92–93% ee.86 The activity was superior to
that of a comparable homogeneous system. The membrane
could be reused. Salts of BINOL with titanium, ytterbium,
and zinc have been used as chiral acid catalysts.87 Hetero-
bimetallic alkoxides derived from two molecules of BI-
NOL, one trivalent metal ion, such as a rare earth, and one
alkali metal ion are chiral basic catalysts.88
Chiral oxidations are important in synthesis. An exam-
10.41
10.42
Chapter 10
ple that illustrates the use of electricity to replace a reagent,
and an insoluble catalyst for ease of workup, is shown in
10.40.89
The use of enantioselective epoxidation is common.90
Chloroperoxidases have been used with hydrogen peroxide
or tert-butylhydroperoxide to epoxidize olefins (10.41) to
epoxides with 88–96% ee.91
The use of hydrogen peroxide with a poly(leucine) cat-
alyst (10.42) offers a simple workup.92 The catalyst can be
reused.
Stereochemistry
10.43
Use of poly(L-leucine) gives the other isomer. Sodium
perborate can also be used as the oxidant. This type of start-
ing material can also be oxidized using hydrogen peroxide
or tert-butylhydroperoxide with La, Y, or Yb-BINOL cat-
alysts in the presence of a molecular sieve to give compa-
rable stereospecificity without the poly(leucine), but re-
covery of the catalyst for reuse is more difficult.93
Jacobsen and co-workers have devised highly enan-
tiospecific manganese complexes for epoxidations of
olefins with sodium hypochlorite.94 Peracids and amine N-
oxides can also be used as oxidants. A typical catalyst is
shown in 10.43:
(The trans-1,2-cyclohexanediamine used in this com-
plex also has been used in a variety of chiral reagents and
ligands for asymmetrical cyclopropanation, alkylation, di-
hydroxylation, and such95). Merck and Sepracor have de-
veloped a drug synthesis based on such a system (10.44).96
10.44
307
Jacobsen and co-workers have used similar catalysts in the
enantioselective opening of epoxide rings. Stereospecific
hydrolysis with a cobalt acetate chelate can be used to re-
solve racemic epoxides.97 Propylene oxide was opened
with trimethylsilylazide in the presence of a RR-chromium
azide chelate catalyst to produce (S)-1-azido-2-trimethyl-
siloxypropane in quantitative yield with 97% ee.98 Cyclo-
hexene oxide was opened with benzoic acid in the presence
of 1 mol% cobalt chelate catalyst to give the hydroxyben-
zoate in 98% yield with 77% ee.99
The Jacobsen epoxidations have also been carried out
with the manganese chelate being made in zeolites.100 No
manganese leached out. These reactions have been some-
what slower and have often tended to give somewhat lower
ee’s. Polymeric versions of the Jacobsen catalyst have also
been used, but have often given lower ee’s.101 Use of a Ja-
cobsen catalyst occluded in a cross-linked poly(dimethyl-
308
10.45
siloxane) membrane reactor gave 78% conversion to a
product with 57% ee in 8h.102 Thus, further work is needed
to improve these systems, which offer easy recovery of the
catalyst for reuse.
A disadvantage of the Jacobsen methods is that they are
energy-intensive because low temperatures (0°C to as low
as 78°C) are often required for optimal stereoselectivity.
As pointed out in Chap. 4, the ligands in metal chelate cat-
alysts often undergo oxidation themselves, shortening the
useful lifetimes of the catalysts, although encapsulation in
a zeolite can slow this oxidation. It would be interesting to
see if a completely inorganic catalyst could be devised for
the epoxidations. A manganese derivative of a heteropoly-
acid might work.
Sharpless and co-workers have devised an enantiospe-
cific oxidation of allylic alcohols to the epoxides using tert-
butylhydroperoxide in the presence of titanium(IV) iso-
propoxide and dialkyl tartrates (10.45).103
10.46
10.47
Chapter 10
The Sharpless group is best known for development of
a method for the asymmetrical dihydroxylation of
olefins.104 A typical oxidation uses 1 mol% of potassium
osmate dihydrate, 1 mol% ligand, potassium carbonate,
potassium ferricyanide, and methylsulfonamide in aqueous
tert-butyl alcohol. Other oxidants such as N-methylmor-
pholine-N-oxide can be used in place of the potassium fer-
ricyanide. One of the preferred ligands is a bis(dihydro-
quinidine ether) of phthalazine (10.46).
Reaction 10.47 was run with the amine oxide.
The method gives higher enantioselectivity with trans-
than with cis-olefins.105 Catalytic asymmetrical aminohy-
droxylation of double bonds (10.48) can be done by a mod-
ification of the method using chloramine-T.106
Frequently, the hydroxysulfonamide crystallizes out of
the reaction mixture so that it is easily recovered by filtra-
tion. Substitution of benzyl-OCONCINa for the chlo-
ramine-T raised the yield as high as 80% and the ee as high
as 99%.107
Because the molecular weight of the ligand is relatively
large, 1 mol% of it amounts to quite a bit on a weight basis.
As it is expensive, a convenient method of recovering it for
recycle is needed. The dihydroxylation of an alkyl cinna-
mate was carried out in 81% yield and more than 99% ee
with a phthalazine-alkaloid catalyst attached to silica.108
Another silica-supported catalyst gave 92% yield and 97%
ee in the dihydroxylation of styrene.109 The catalyst could
be reused seven times with no loss of ee, but small amounts
Stereochemistry
10.48
of potassium osmate had to be added with each cycle. Poly-
meric derivatives of cinchona alkaloids have also been
used for ease of recovery by filtration.110 One of these cat-
alysts could be reused three times with no loss in activity.
The ee was 88%. Another gave an 86% yield and 65–97%
ee in the dihydroxylation of styrene.111 It could be used five
times more if a little more osmium was added at each cy-
cle. A better system that does not sacrifice any enantiose-
lectivity uses a soluble polymer and gives up to 99% ee
with 86–92% yields.112 The ligand is attached to polyethy-
lene glycol monomethyl ether (10.49).
At the end of the reaction, addition of tert-butyl methyl
ether precipitated the polymer, which was removed by filtra-
tion, the product remaining in solution. The recovery of the
polymer was 98%. It could be used repeatedly with almost
no change in enantioselectivity or yield. (The use of ultrafil-
tration to separate the polymer would eliminate the need for
the tert-butyl methyl ether.) A similar dihydroxylation in
which the cinnamate substrate was part of an insoluble poly-
10.49
309
mer gave 98% ee at 98% conversion.113 The phthalazine–al-
kaloid catalyst was attached to a soluble polymer. Ideally,
the osmium compound should remain on the polymer with
no losses, or if soluble polymers are used, be easy to separate
for reuse from the filtrate from ultrafiltration. Microencap-
sulated osmium tetroxide is now available.143
The Sharpless epoxidation of allylic alcohols with tert-
butylhydroperoxide and titanium(IV) isoproxide has been
carried out with a polymeric tartrate made from tartaric
acid and 1,8-octanediol.114 The yield of epoxide (92%) was
comparable with that when dimethyl tartrate was used
(91%), but the 79% ee was lower than the 98% ee found
with the dimethyl tartrate. It may be possible to raise the ee
by further variations in the structure of the polymer. The
heterogenization of a catalyst for a homogeneous reaction
often requires optimization to obtain comparable or higher
yields and stereospecificity.
The toxicity of the osmium compounds is worrisome.
They are also expensive. Ruthenium has been used in place
310
10.50
of osmium, but its compounds can also be toxic and ex-
pensive.115 Because potassium permanganate is also used
in the dihydroxylation of double bonds, manganese com-
pounds should be tried with asymmetrical ligands. This
may be a good place to use combinatorial chemistry. In
view of the recent use of titanium silicates in oxidation re-
actions (see Chap. 4), titanium compounds should also be
screened. The ideal would be to find an asymmetrical com-
pletely inorganic compound that would do the job. The cost
of the oxidizing agent can be minimized by regenerating it
electrochemically.116
Many asymmetrical reactions are carried out to form
carbon–carbon single bonds. Addition of triethylaluminum
to benzaldehyde in the presence of (S)-octahydroBINOL
gave the alcohol addition product (10.50) in 100% yield
and 96.4% ee.117
10.51
10.52
Chapter 10
An interesting specialized case involves asymmetrical
autocatalysis in which the product of the reaction is the
ligand (10.51).118 The reaction is seeded with 98.8% ee
product.
If the reaction is seeded with leucine of 2% ee, the
reaction product has 21–26% ee, and if seeded with 2-bu-
tanol of 0.1% ee the reaction product has 73–76% ee.
Using either of these products as seed for a repeat
run raises the ee to more than 95%. Similar chiral ampli-
fication is seen in the addition of diethylzinc to benzalde-
hyde in the presence of a diaminoalcohol (10.52),
with 15% ee where the product formed has an ee of
95%.119 (Such effects have also been seen in several other
reactions.)
Chiral Lewis acids derived from tartaric acid have been
used in the asymmetrical addition of dialkylzinc com-
Stereochemistry
10.53
pounds to aldehydes120 and nitroolefins (10.53).121 An-
other chiral Lewis acid has been used to catalyze the reac-
tion of aldehydes with allyltrimethylsilane (10.53).122
An analogue of the second catalyst, where F is replaced
by O-i-C3H7, has been used to catalyze the reaction of ben-
zaldehyde with a silyl enol ether (10.54).123
The enantioselectivity was much poorer in the noncoor-
dinating solvents, methylene chloride and toluene. Thus, it
is important to remember that solvents can coordinate with
a metal center in the transition state and play an important
role in determining selectivity.
Bisoxazoline copper complexes have also been used as
chiral Lewis acids that give high yields and enantioselec-
tivities (10.55).124
The enantioselectivity can vary with the anion. With a
10.54
311
related copper chelate, the hexafluoroantimonate was a
more enantioselective catalyst than the trifluoromethane-
sulfonate. This shows that anions are more than innocent
bystanders. Copper bisoxazoline complexes have also been
used in asymmetrical Diels–Alder reactions125 and ene re-
actions.126 The activity is said to approach that of enzymes.
When runs were made in hexane in the presence of florisil,
the catalyst could be recovered by filtration and reused with
only a slight reduction of activity. Various Lewis acids of
magnesium,127 tin,128 titanium,129 and boron130 have also
been used as catalysts for such reactions. An asymmetrical
Diels–Alder reaction with an aluminum Lewis acid is
shown in 10.56.131
Chiral bases are also used in asymmetrical synthesis. An
alkylation is shown in 10.57.132
312 Chapter 10

10.55

10.56

10.57

Another chiral base that has been used is potassium N-

methylephredinate (10.58).133
Chiral bases made by treatment of (R)-BINOL with a
combination of lanthanum isopropoxide and sodium tert-
butoxide have been used in asymmetrical Michael reac-
tions to produce products with 92% ee.134
Chiral phase transfer catalysts have been used in the
synthesis of amino acids (10.59).135 (The amino acid is ob-
tained by hydrolysis of the product shown.) This type of 10.58
Stereochemistry
10.59
10.60
catalyst has also been used successfully in the epoxidation
of --unsaturated ketones in toluene with aqueous
sodium hypochlorite.136
Efforts are being made to simplify the workups and the
recovery of the chiral ligands for recycling by the use of
polymeric reagents. In some cases this works well, but in
others, optimization is needed to make the results as good
as those in solution. Asymmetrical protonation with a poly-
mer-supported chiral proton donor (10.60) has given better
results than the comparable reaction in solution.137 The
10.61
313
polymer puts additional steric constraints on the system,
which in this case are favorable.
The product is obtained in 95% yield and 94% ee.
In the counterpart in solution, the ee was only 21–50%.
Polymeric chiral catalysts have also been used in the
addition of zinc alkyls to aldehydes. Use of a proline-
based copolymer in a continuous asymmetrical synthesis
with an ultrafiltration membrane gave 80% ee (10.61).138
There was no deactivation in 7 days. A boron-contain-
ing polymer (10.62) gave only 28–51% ee compared with
the 65–75% ee found with model compounds in
solution.139
Further work with supported catalysts in membrane re-
actors is needed to raise the enantioselectivity to commer-
cially useful levels. Care should be used to pick supports,
polymers or otherwise, that are very stable under the con-
ditions of the reaction so that they will be longlived.
Many other types of reactions have been used in asym-
metrical syntheses. A rhodium-catalyzed allylic rearrange-
ment (10.63) has been used to make 1000 metric tons of
()menthol per year.140
10.62
314
10.63
The rhodium catalyst gives 400,000 turnovers. A draw-
back of the route is the need to recrystallize the isopulegol
at 50°C to achieve 100% ee. Other asymmetrical reac-
tions include hydroformylation, hydrocyanation, cyclo-
propanation, aziridination, and so forth. The various sug-
gestions for improvement of the reactions discussed in this
chapter can be applied to these also. It would be preferable,
if possible, to avoid the use of toxic hydrogen cyanide al-
together. Extensive work has gone into fine-tuning the met-
allocene catalysts used for the stereospecific polymeriza-
tion of olefins.141 Perhaps some of the principles used there
can be applied here, too.
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Chapter 10
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Recommended Reading
1. S Kotha. Tetrahedron 1994; 50:3639.
2. SC Stinson. Chem Eng News 1998; Sept 21: 83.
3. G Kaupp. Angew Chem Int Ed Engl 1994; 33:728–729.
EXERCISES
1. See what chiral chemistry is being done at your
school or industrial laboratory. What methods are
being used? Are the chemists aware of some of the
less wasteful approaches mentioned in this chapter?
2. Look up chiral inorganic compounds that do not
contain carbon. How would you make such a com-
pound that would be an oxidation catalyst with a
long lifetime? (Many oxidation catalysts fail be-
cause of oxidation of the organic ligands on the
metal ion.)
3. Devise a system for a Sharpless dihydroxylation of
an olefin in which no osmium or alkaloid-derived
ligand is lost on repeated reuse. You may want to
refer to Chaps. 5 and 7 for hints.
11
Agrochemicals

I. THE NATURE AND USE OF are broad-spectrum insecticides that can be very toxic to
AGROCHEMICALS beneficial insects.8
DDT [1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane:
Agrochemicals include fertilizer, fungicides, herbicides, (11.2)], also called dichlorodiphenyltrichloroethane, was
and insecticides. The last three are pesticides.1 The world introduced about the time of World War II. This was fol-
used 2.1 billion kg of pesticides in 1995.2 Of this total, lowed by a flood of many other highly chlorinated hydro-
10–25% is used on one crop, cotton.3 carbons, including toxaphene (11.3).
Most of these have since been banned in the United
States and many other countries, although they are still
U. S. market World market used in some.9 They caused reproductive failure in birds,
(in millions of kg of active ingredient) such as the bald eagle, osprey, pelican, and peregrine fal-
con, owing to eggshell thinning; DDT is a human carcino-
Herbicides 301 1002 gen. Toxaphene was very toxic to fish, the median lethal
Insecticides 153 767 concentration (LC50) for trout and blue gill is 0.003–0.005
Fungicides 74 256
ppm, and for birds, it is 40–71 mg/kg.
Other 40 107
The organophosphate insecticides, such as malathion,
Total 568 2132 (11.4) came next. These are less persistent in the environ-
ment, but more toxic to humans. Carbamates, such as car-
baryl, (11.5) were also introduced.
The U. S. total in 1995 was a record high.4 Pesticides are Carbaryl is made by the reaction of methylisocyanate
used on 900,000 farms and by 69 million households in the with 2-naphthol. This is the product made at the plant in
United States.5 The herbicide, atrazine, was the one used in Bhopal, India where the disaster mentioned in Chap. 1,
the largest amount, 32 million kg. occurred.
Early insecticides were often inorganic arsenic, copper, Newer insecticides being introduced today may be more
lead, and sulfur compounds.6 An example is Bordeaux selective and less toxic to nontarget organisms.10 For
mixture, which contains copper sulfate and calcium hy- example, the insecticide pirimicarb (11.6) is highly selec-
droxide. Copper chromium arsenate is used today as a tive for aphids and has little effect on biological control
wood preservative. Organic natural products, such as organisms.11
pyrethrin and rotenone (11.1) have also been used. The first synthetic herbicide12 was 2,4-dichlorophenoxy-
Rotenone is used today for killing undesirable fish, such as acetic acid (11.7). The one used in largest volume today is
carp, before restocking ponds with game fish. Many syn- atrazine, which is typical of a group of triazine herbicides.
thetic pyrethrins are used today because of their relative Glyphosate (very low mammalian toxicity) is used exten-
safety to humans. However, both rotenone and pyrethrin7 sively to kill vegetation nonselectively.13 Alachlor is a typ-

319
320 Chapter 11

11.1

11.2

11.3

11.6

ical amide herbicide. Trifluralin is representative of the

dinitroanilines. Paraquat (very toxic to humans) is used ex-
11.4 tensively to kill vegetation before planting a new crop in
no-till agriculture.14 This practice reduces soil erosion
greatly.
Two newer classes of herbicides are active at much
lower dosages. The sulfonylureas (11.8)15 are used at 2–4
g/ha. The sulfonylureas have low mammalian toxicity.
Only 1.4 oz/acre of the imidazolinones (see 11.8)16 is
needed.
The herbicide flumiclorac (11.9), for use on maize and
soybeans, is neither a teratogen nor a carcinogen. It hy-
drolyzes too quickly to contaminate groundwater.17 (This
will only be effective as long as the hydrolysis products are
11.5 nontoxic.)
Agrochemicals
11.7
11.8
11.9
Typical fungicides (11.10) include sulfur, Bordeaux
mixture, dithiocarbamates, captan, and benomyl.18
Fertilizers are usually simpler compounds that supply
nitrogen, potassium, and phosphorus to plants.19 Typical
compounds are potassium chloride, ammonium nitrate, di-
321
ammonium phosphate, and urea–formaldehyde conden-
sates. The last are for slow release.
Controlled release of agrochemicals (e.g., by hydroly-
sis of a polymeric ester) can offer the advantages of con-
stant level, smaller dose, reduced evaporation loss, lower
toxicity, longer life, decreased environmental pollution,
and reduced effect on nontarget species by wind or
runoff.20 Systemic pesticides are preferred. This ensures
protection of the growing tip of the plant. For weed
killers, this means that it is not necessary to hit every leaf
of the plant with the herbicide. Pesticides are often ap-
plied on a spray schedule according to the calendar as a
prophylactic measure. Chemical pesticides are used 98%
of the time.
322
11.10
II. PROBLEMS WITH AGROCHEMICALS21
A. Resistance to Pesticides
The selection of organisms to withstand unusual environ-
ments was discussed in Chap. 9. The organism was chal-
lenged with the reagent or new conditions. The few percent
that survived were challenged again. The process was re-
peated until the organism developed resistance to the chal-
lenge.22 This is exactly what has happened in the use of
pesticides. There are now about 500 species of insects and
mites, 100 species of weeds, and 150 plant pathogens that
are resistant to pesticides that formerly controled them.23
When resistance develops in a pest species, the farmer’s
first response is to increase the dosage. When this no longer
works, he switches to another pesticide or mixture of pesti-
cides. At some point, this no longer works, and the crop can
no longer be raised in the location in question.
The mechanisms of resistance can vary. In bacterial re-
sistance to antibiotics, these include pumping the antibiotic
out of the cell, changing the cell wall to avoid the antibiotic,
enzymatic destruction of the antibiotic, and the develop-
ment of substitute proteins not targeted by the antibiotic.24
It may take longer to develop resistance in insects and
plants than in microorganisms simply because the genera-
tion times are longer.
The best way to avoid the development of resistance is
to devise other methods of controlling the pest, where pos-
sible, and to use the pesticide as a last resort, when nothing
else works. When possible, a variety of approaches that in-
volve different mechanisms can be rotated.
B. Effects of Pesticides on Nontarget Organisms
The ideal pesticide would affect only the one pest species
and nothing else. In practice, this is almost never possible.
Only a few insect viruses (baculoviruses)25 are this spe-
Chapter 11
cific. In designing a pesticide, one looks for a difference
between the metabolism of the pest and everything else. An
insecticide that attacks a metabolic route in insects that is
not present in humans or other mammals should be less
toxic to the latter. An herbicide that interferes with a plant
process not found in animals (e.g., photosynthesis) should
be less toxic to animals. In practice, many of these differ-
ences have not been enough to protect humans and other
animals from the toxicity.26 Rachel Carson was among the
first to point this out.27
It is estimated that there are 1 million pesticide poison-
ings in the world each year.28 These are more likely to hap-
pen in the developing world where fewer precautions are
taken when spraying. China had 10,000 deaths in 1993.
The United States exports many pesticides that are banned
or restricted in this country.29 About three-fourths of these
exports lacked chemical-specific information. The U.S.
Environmental Protection Agency (EPA) received 1500 re-
ports of adverse effects of pesticides covering 9200 inci-
dents in 1996.30 Organophosphate and carbamate insecti-
cides inhibit cholinesterase, which is present in humans as
well as in insects. They can cause headaches, nausea, dizzi-
ness, vision problems, and other discomforts.31 The carba-
mate insecticide, carbaryl, may be linked to some cancers
in the United Kingdom.32 An epidemic of nearsightedness
in Japan in the late 1950s to the early 1970s may be linked
to the use or organophosphate insecticides.33 Some farmers
want organophosphate sheep dips to be banned, because of
their neuropsychological effects on humans.34 Organo-
phosphate and carbamate insecticides are under review by
the EPA to see if additional restrictions should be placed on
their use.35
Certain tumors are more common among farmers.36
Cancer has been correlated with maize production in the
Midwest and with cotton and vegetable growing in the
southeastern United States. Farmers have an increased in-
Agrochemicals
cidence of non-Hodgkin’s lymphoma, an often fatal form
of cancer.37 There is also evidence that some widely used
pesticides can suppress the immune system and lead to
more illnesses.38 Indirect detrimental effects of pesticides
may go unnoticed or be hard to pin down. Pesticides are
now being evaluated as endocrine disrupters,39 as men-
tioned in Chap. 3. The natural insecticides sometimes used
in organic farming can also be harmful. Ingestion or in-
halation of sabadilla can cause gastrointestinal symptoms
and hypotension (low blood pressure).40 The problems of
nicotine are well known.
Misuse of pesticides can occur. Methyl parathion
(11.11) is an insecticide that is permitted for use on crops
outdoors, but is banned from indoor use. It was used for
control of cockroaches in 2700 houses in Mississippi and
surrounding states in 1996. About 330 families had to be
evacuated from their homes. Decontamination is ex-
pected to cost 50 million dollars.41 Ironically, some peo-
ple in Louisiana deliberately sprayed their homes with
methyl parathion to obtain “free” repairs. As mentioned
in Chap. 1, pesticide residues on foods are monitored and
are not normally a problem. However, there have been
some instances of pesticides used illegally on food
crops.42 This tends to happen more often on foods im-
ported into the United States and Canada from developing
nations.43
Pesticides harm or kill many nontarget organisms.
These include bats, birds, and fish, which often eat insects.
Agricultural chemicals may also be part of the reason for
the recent decline in amphibian populations, either directly
or indirectly, by making the weakened animals more sus-
ceptible to disease and parasites.44 Beneficial insects that
may prey on the pest species are also killed. The killing of
zooplankton by low levels of pesticides in agricultural
runoff is thought to be responsible for some algal blooms in
the Netherlands.45 There is now a shortage of natural polli-
nators in some places as a result of pesticide use.46 Some
plants no longer have pollinators. The answer is not just to
bring in more hives of honeybees. They too have been
harmed by pesticides. They are not efficient pollinators for
many plants, including crops such as alfalfa and lima
beans. The killing of earthworms reduces soil tilth, includ-
ing the ability of air and water to penetrate the soil. The use
of herbicides also destroys soil tilth and can promote loss
11.11
323
of topsoil through erosion. They can reduce erosion if used
in no-till farming, which makes plowing unnecessary.
Antibiotics are used routinely in feeds for animals, such
as cattle, hogs, and poultry, to promote growth and prevent
disease.47 The problem is that this type of “directed evolu-
tion” has produced strains of bacteria that cause human dis-
eases that are resistant to antibiotics. Escherichia coli
O157:H7, which is present in 2% of cattle, causes 20,000
cases of illness, including 250 deaths, in the United States
each year.48 A vaccine is being developed for it. A simpler
way to avoid this strain is to feed the cattle with hay instead
of grain for the last 5 days before slaughter.49 (The acids
formed in the colon of the cattle from digestion of the
starch in the grain causes the development of strains that
are resistant to the stomach acid of humans.) The European
Union has banned virginiamycin, spiramycin, tylosin phos-
phate, and bacitracin zinc from animal feeds.50 Sweden
banned antibiotics from animal feeds in the 1980s. It has
substituted better hygiene on the farm for the antibiotics.
C. Pesticides and Fertilizers in Air and Water
Pesticides do not always go where they are intended to go
and, if they do, they do not always stay there. In aerial
spraying, 50–75% of the spray can miss the target.51 If the
insecticide lands on areas adjacent to the field it can harm
natural insect pollinators and predators. If an herbicide
lands on adjacent areas, it can kill vegetation that is the
home of natural predators and pollinators. Sensitive crops
in adjacent fields can be killed. If the crop is young, most
of an insecticidal spray ends up on the ground.
Rain may also wash some of the spray off the leaves.
Most pesticides are not compounds with high molecular
weights. They can evaporate in the heat of the sun. Once
airborne, they can travel to remote parts of the world,
where rain can bring them to the surface again.52 This long-
range aerial transport explains how remote lakes in the Arc-
tic and remote islands in the oceans have become contami-
nated. The preemergence herbicide, acetochlor (11.12),
11.12
324
11.13
was detected in 29% of rain samples at four sites in Iowa
and in 17% of stream samples from 51 sites in nine states.53
A study of ambient air in California showed that concen-
trations of 1,3-dichloropropene and methyl bromide (used
as soil fumigants) were high enough in some places to be of
concern.54 Some of the herbicide put on the lawn can be
tracked into the house, where it can become carpet dust.55
The pesticide can enter the ground with rains. It can re-
main intact or be degraded to metabolites that may or may
not be toxic. Rain can also carry some of it into the nearest
lake or river.56 Fertilizers can be moved in the same way.
They can cause eutrophication of lakes and rivers. Ground-
water contamination57 by farm or ranch runoff has been re-
ported in 44 states in the United States.58 Half of the wells
for drinking water in the United States contain nitrates. (Ni-
trates can come from fertilizers or animal wastes. In suffi-
cient amounts, they can cause depletion of oxygen in the
11.14
Chapter 11
blood of infants.) The average annual loss of soil from
farmland is 5 ton/acre. Some 14 million Americans are rou-
tinely exposed to weed killers in their drinking water.59
Atrazine is the most commonly used herbicide. Although,
only 1–2% may be lost from fields into rivers, this is
enough to kill some aquatic plants.60 At high doses,
atrazine triggers mammary tumors in susceptible mice.61 It
can cause chromosomal breaks in Chinese hamster ovary
cells at a level of 3 ppb.62 Chlorotriazines,63 such as
atrazine, have been shown to be endocrine disrupters.
Atrazine is not removed from drinking water by conven-
tional water treatment.64 Polymeric analogs of atrazine,
copolymers of acrylamide and allyltriazines, solve the
problem of evaporation into the air and may be less likely
to get into ground and surface water. One of them is shown
on 11.13. They are effective herbicides.65
It is common for the metabolite of the pesticide to be
found more frequently than the pesticide itself.66 The level
of atrazine in groundwater was half that of its metabolites.
Metabolites found in a stream included hydroxyatrazine,
deethylhydroxyatrazine, and deisopropylhydroxyatrazine
(11.14).67 The half life of atrazine in the soil to give non-
phytotoxic products varies from 60 days to more than a
year.68 The herbicide alachlor is present at low levels in
groundwater in 16 states. It is classed as a “probable human
carcinogen.” It is degraded to a variety of products in soil
(11.15). Some of these are weak mutagens.69
D. Sustainable Agriculture
Sustainable agriculture70 can be defined as a system that
indefinitely meets the demands for agricultural output at
Agrochemicals
11.15
socially acceptable economic and environmental costs.71
Another group says that sustainable agriculture involves a
system for food and fiber production that can maintain high
levels of production with minimal environmental impact
and can support viable rural communities.72 It conserves
natural resources. The present system of agriculture in the
United States is unsustainable. It is the most energy-inten-
sive system in the world.73 Not only is fuel needed for the
machines that plow the ground, sow the seed, cultivate,
spray, and harvest the crop, and carry it an average of 1400
miles to the consumer, but also to make the fertilizer and
pesticides used on the farm. For example, the synthesis of
ammonia (11.16) is energy-intensive; it is based on fossil
fuels and produces carbon dioxide, which is involved in
global warming. The hydrogen for the process is derived
from natural gas or petroleum.74 Natural gas accounts for
70% of the cost of making ammonia.75
CH 4  H2O 
Ni catalyst
 → CO  3 H2
700–830°C.
Fe catalyst
CO  H2O 425°C.
 → CO2  H2
Fe catalyst
N2  3 H2  → 2 NH3
400–600°C.
85–90% yield at 20–22% conversion
11.16
One reason for the high energy consumption is that the exit
gases from the ammonia synthesis must be cooled to 10
to 20°C to condense out the ammonia, then reheated for
325
recycle. Sustainable agriculture should have a minimum of
external inputs.
Crop losses caused by insects went up from 7 to 13% in
the period from 1945 to 1989, despite the use of ten times
as much insecticide in 1989.76 The reasons probably in-
volve the shift to intensive monoculture and the loss of nat-
ural predators. As mentioned earlier, the lack of specificity
and the toxicity of insecticides are problems that need to be
solved in a system of sustainable agriculture.
The loss of topsoil must be reduced greatly so that the
agricultural productivity does not decline. The cost of soil
erosion in the United States has been estimated to be $44
billion/yr.77 This includes the cost of nutrients that have to
be replaced with more fertilizer and the damage caused by
the silt in the rivers. It cost $28/yd3 to dredge the harbor of
Green Bay, Wisconsin. There was some thought of selling
this topsoil back to the farmers. This idea was abandoned
when it was found that putting 35 to 66-ft buffers of grass
on each side of the stream could keep the soil out of the har-
bor for $2/yd3.78 The U. S. Department of Agriculture has
a new policy of paying farmers to put in such buffers to re-
duce the amount of soil, fertilizers, and pesticides entering
streams.79 Fertilizer runoff from midwestern farms in the
United States has caused oxygen depletion ( 2 mg/L dis-
solved oxygen) in 18,000 km2 of the Gulf of Mexico.80
(This dead zone is exceeded in size only by dead areas in
the Baltic and Black Seas.81) This has an effect on the
Gulf’s fisheries. Fertilizer runoff is also a problem in
restoring the health of Chesapeake Bay in Maryland. 82
Soils in natural areas are often rich in organic matter. They
326
have a porous structure which allows rain to infiltrate read-
ily, decreasing runoff. This soil structure is lacking in con-
ventional agriculture using herbicides and synthetic fertil-
izers. It is present when organic farming is used.83 (This
involves returning all crop residues and animal waste to the
land.)
Humans have used a great many species of plants for
food over the millenia. However, most agriculture in the
United States today is based on about two dozen crops.
Many of these older food crops need to be reinvestigated to
look for more nutritious ones that can thrive with little in-
puts of fertilizer, pesticide, and water.84 Many of our major
crops are annuals, so that plowing (minimized in the no-till
system) and reseeding are needed every year. Some groups
are investigating perennial crops to give sustainable yields
with minimal soil erosion.85 Current efforts are focused on
breeding for higher yields.
The EPA has joint programs with the U. S. Department
of Agriculture (USDA) and some growers to minimize the
use of pesticides.86
As the world’s fisheries have declined, attention has
turned to aquaculture. For it to be sustainable in the future,
current problems of replacement of mangroves by ponds,
use of wild fish as feed, pollution from wastes, escapes of
exotic species or varieties, and the short lifetimes of ponds,
must be solved.87 Shrimp and salmon farming have many
of these problems. It would be better to farm herbivorous
fish.
III. ALTERNATIVE AGRICULTURE
The field of alternative agriculture is covered by several
books and reviews,88 from which much of the following
discussion has been taken. Many standard agricultural
methods disrupt the natural processes that suppress pests.89
Crop monocultures tend to invite pests, especially when
there is no alternate food and when their natural enemies no
longer have places to live. The increased mechanization of
agriculture has resulted in the removal of many hedgerows
where these natural enemies as well as natural pollinators
could live. The use of herbicides and synthetic fertilizers
instead of cover crops and organic fertilizers, together with
application of fungicides and insecticides, has resulted in
much less life in the soil, as well as to soil erosion. Some of
the organisms in a healthy soil90 can be very beneficial in
controlling pest species. The key to alternative agriculture
is a thorough understanding of the ecology of the crop, the
pests, and their natural enemies. This requires a great deal
of study and monitoring of populations. The various ap-
proaches to the control of pest populations are grouped in
the following under the categories of insects, weeds, fungi,
Chapter 11
and such. In some cases, an approach can apply to more
than one group. In addition, many new crop protection
agents or leads for them can come from studies of natural
products.91
A. Insects and Other Animals
1. Mechanical and Cultural Methods
The first approach should be to plant a variety of the crop
that has been bred to be resistant to the pest. Unfortunately,
a general confidence in chemical methods of control has
slowed the breeding of resistant varieties. Some insects can
be removed mechanically. Hand picking is done in some
home gardens. A vacuum cleaner can remove insects from
lettuce.92 Unfortunately, this system has not proved effec-
tive with other crops. Not all mechanical traps are effective.
A popular type for the control of biting flies uses an ultra-
violet light to attract insects to an electrified grid. A study
in northern Delaware found only 31 biting flies (0.22%) in
a total of 13,789 insects from such traps.93 The nontarget
insects were from 104 insect families. There were 1868
natural predators and parasites94 present in the sample.
Many mosquitoes are not attracted to light, but are to the
carbon dioxide emitted by an animal. Not only is the trap
ineffective, but it is a threat to insect biodiversity. A trap
with carbon dioxide plus octenol (a component of cow’s
breath) was much more effective.95 The mosquitoes were
killed by the synthetic pyrethroid insecticide in the trap.
(Carbon dioxide has also been used to lure sand flies to a
trap where they were caught on fabric panels coated with
mineral oil.96) Mosquito populations can be reduced by
eliminating standing water where they can breed (e.g., gut-
ters that do not drain well). For ponds and marshes, making
them more accessible to small mosquito-eating fish can
help. Animals that eat mosquitoes should be encouraged,
(e.g., bats, nighthawks, swallows, frogs, and dragonflies)97
Insects in grain can be killed by microwaves as the grain
enters the grain elevator.98 Because there is more water in
the insects than in the grain, they heat up first. Passing in
air at less than 17°C also deters the insect feeding.99
Barn owls have been used for effective rat control in
palm oil plantations in Malaysia.100 Putting up nest boxes
helps to attract the one barn owl needed for each 10 ha. The
introduction of the mongoose into Hawaii to control rats
was a disaster. The mongoose is diurnal, the rat nocturnal,
so that the two do not meet. However, the mongoose has
decimated some of the bird species on the islands.101
Crop rotations can be a valuable way to disrupt a pest’s
life cycle. (They also increase profitability.102) The soy-
bean nematode is a problem if the farmer tries to grow the
same crop in the same field year after year. If corn is
Agrochemicals
11.17
planted in alternate years, the nematode eggs die out and
there is no problem.103 A Pasteuria bacterium, added to the
soil, can also help control this nematode.104 In England,
control of a cyst nematode was disrupted when the farmer
applied a fungicide to his crop and killed the soil fungi that
controlled the nematode. Other strategies for controlling
the soybean nematode involve use of compounds (11.17)
that inhibit the hatching of the eggs or which stimulate
them to hatch when there is no crop for them to feed on.
The compound on the left gave 87% control of hatching
at 54  g/L. That on the right stimulated hatching at as low
as 1012 G/L. A potato cyst nematode, normally controlled
by carbamates, organophosphates, or methyl bromide, can
be controlled by trans-1,3-diphenylpropenone (11.18),
which kills the nematodes as well as inhibits hatching. It
has low oral toxicity (to mice) and low phytotoxicity.105
It also helps destroy the insect or its eggs when it is over-
wintering. Crop residues are sometimes burned to do this.
A better system, which avoids the air pollution associated
with burning, is to compost the crop residues.106 If done
properly, the temperature in the compost pile is enough to
destroy insects, fungi, and weed seeds. The compost can
then be put on the fields to increase the organic matter of
the soil.
Intercropping is a useful technique.107 Trap crops can
lure the pest away from the main crop. Alfalfa has been
11.18
327
used to keep lygus bugs off cotton in this way. Squash has
been used to keep squash bugs and cucumber beetles off of
watermelon and cantaloupe. After the insects collect on the
squash they can be sprayed without harming the beneficial
insects in the area.108 Weeds can take nutrients and sunlight
intended for the crop. However, the presence of weeds can-
not be judged to be detrimental automatically. There are
some instances where they are beneficial to the crop and
should not be mown until they clearly interfere with the
crop yield. Several mechanisms are operative. Morning
glories controlled the Argus tortoise beetle in sweet pota-
toes by serving as an alternative host for a parasite for the
beetle. Wild mustard in broccoli served as a trap crop for
Phyllotrea cruciferae. Eleusine indica and Leptochioa fil-
liformis kept leaf hoppers off of beans by chemical repel-
lency or masking. When beans are intercropped with
wheat, there is impairment in the searching behavior of
aphids. When maize is grown with beans, there is an in-
crease in the numbers of beneficial insects and interference
with colonization. When peanuts and field beans are raised
together, the aphids become trapped on the epidermal hairs
of the beans. Intercropping cabbage with tomato and to-
bacco results in feeding inhibition of flea beetles by the
odors of the nonhost plants. Strongly aromatic plants, such
as onions and tomatoes, can disturb the mechanics of ori-
entation of insects. Extracts of marigolds have been used as
larvicides for the mosquito, Aedes aegypti.109
2. Predators, Parasites, and Pathogens
Natural enemies often keep insect populations under con-
trol. Some of the biggest problems have come from the in-
troduction of animals and plants to new continents without
their natural enemies. There was a tremendous population
explosion of the Japanese beetle in the eastern United
328 Chapter 11

States in the 1930s. It was brought under control by the im-

portation of a fungus (milky spore disease). The state of
Delaware was marked off in a grid pattern. Every square
with grass in it was inoculated with the fungus. Today, the
problem with the beetle is minor. Most introductions to
new continents do not become problems.110 Of intentional
introductions 25–68% have become established and only
2% have become pests. Five percent of unintentional intro-
ductions have become established, but only 7% of these
have become pests. Nine of 20 species of introduced do-
mestic animals have become serious environmental prob-
lems (e.g., pigs and goats in Hawaii). Eleven of the world’s
11.19
worst weeds were crop plants in other regions. Guava and
ginger are noxious weeds in Hawaii. When the natural en-
emies are brought in to control foreign insects and weeds, let light and degradation by proteases, and can be prepared
the return on the investment is 30-fold. Great care must be by low-cost methods.118 Care should be taken not to
used to be sure that the natural enemies will not choose to overuse it, as Culex mosquitoes can become resistant to it.
attack any other species. Sterile male release can be used to The fungus Beauveria bassiana is used to control in-
wipe out a relatively small population of a new introduc- sects in turf and flies in cattle sheds.119 This and another
tion. Large numbers of sterile males must be released to fungus (Paecilomyces fumosoroseus) kill white flies that
stamp out the wild ones. This technique was successful in are resistant to chemical pesticides.120 When freeze-dried
eliminating the screw worm fly from the southeastern and stored, there is 70% survival after 5 months. The ento-
United States. It has also been used to eliminate the tsetse mopathogenic nematode genera, Steinernema, Psammo-
fly from Zanzibar.111 mermis, and Heterorhabditis have also been used on soil
Many predators, parasites, and diseases of problem insects.121 The actual killing of the host is done by bacteria
species112 can be encouraged by providing them with that are symbiotic with the nematodes.122 Other nematodes
refuges in which to live. In areas where these local popula- have been used to control houseflies123 and the sap beetle
tions may not exert sufficient control, mass rearing (often on maize.124 The beetle, Rodiola cardinalis, has been used
using synthetic diets113) and timely release into the fields to control cottony cushion scale of citrus.125 Many parasitic
may solve the problem. A few of many examples will be organisms (e.g., wasps that lay their eggs on insects), are
given.114 Beneficial mites are used to control the two-spot- highly host- and habitat-specific.
ted spider mite on 50–70% of California strawberries. The Many baculoviruses126 (i.e., insect viruses) are species-
protozoan Nosema locustae is used to control grasshop- specific. They have been used for the successful control of
pers. Bacillus thuringiensis is used to control Lepidoptera the gypsy moth, velvet bean caterpillar (on 5.9 million ha
(butterflies and moths). It must not be overused because re- of soybeans in Brazil), cotton bollworm, codling moth (on
sistance to it can develop. Resistance in the diamondback apples, pears, and walnuts), rhinoceros beetle, potato tuber
moth is an example.115 It can also be a problem if it gets on moth, sawflies, and porina moth.127 The gypsy moth was
nontarget Lepidoptera. An area in Oregon where it was introduced into the United States in Massachusetts from
used showed a loss of two-thirds of the species present and Europe in 1869. It defoliates many trees if there are no
a 95–99% decline in the biomass of caterpillars.116 This checks on its population. The “war” against it has often
same problem may result from the use of “Spinosad,” a used diflubenzuron (“dimilin”) (11.20), which affects
mixture of spinosyns A and D (11.19) isolated from the soil many nontarget species.128
bacterium Saccharopolyspora spinosa, if it is used in sim-
ilar situations. It won a Presidential Green Chemistry Chal-
lenge Award in 1999.117
It does not harm most beneficial insects, has a low toxi-
city to mammals and birds, does not bioaccumulate, breaks
down quickly in sunlight, adsorbs to and does not leach
from soils, but still has a broad spectrum of activity against
Lepidoptera. Strains of B. thuringiensis that control
Coleoptera (beetles) have also been found. Bacillus sphaer-
icus works better on mosquitoes because it resists ultravio- 11.20
Agrochemicals
11.21
This type of spraying is thought to have eliminated about
two dozen species of desirable moths and butterflies from
New Jersey. Bacillus thuringiensis is more expensive and
more selective, but still harms other Lepidoptera. The virus
(“Gypchek”) is the most selective. It is just coming into use
for control of the moth. A fungus imported to control the
moth also works in some cases. Small mammals, such as
mice and shrews, also help by eating the larvae. There are
also some less specific insect viruses that can control up to
30 species. Some of the problems in the use of baculoviruses
are limited stability to ultraviolet light, the high pH of some
leaf surfaces, and the slowness of death of the moths. The
first can be improved by the use of ultraviolet screening
agents, such as fluorescent brighteners, sometimes used
with a feeding stimulant.129 Antioxidants also help. Encap-
sulation with starch helps.130 Faster kills of maize earworms
are being obtained by incorporating an appetite-stopping
hormone.131 Large companies often consider such niche
markets too small to warrant their attention.
3. Antifeedants
It is not necessary to kill an insect pest to protect the crop.
Sometimes, repellents will do the job.132 Many plants
11.22
329
have evolved with alkaloids, such as quinine, quinidine,
cinchonidine, strychnine, and brucine (11.21), that deter
feeding.133
Two of the best studied insect antifeedants are
azadirachtin from the neem tree (Azadirachta indica)134
and polygodial from Polygonum hydropiper (11.22).135
Parts of the neem tree have been used in India for food pro-
tection for many years. Neem extracts deter feeding in 135
species and disrupt mating. These include the cockroach,
Mediterranean fruit fly, gypsy moth, and locusts.
Azadirachtin hydrolyzes readily so that it will not be per-
sistent in soils. Its use may be limited somewhat by its sen-
sitivity to acid, base, and ultraviolet light. Its use might be
extended by encapsulation using an ultraviolet screening
agent in the coating. (Abamectin, a natural product pesti-
cide that degrades rapidly in air and sunlight, has been sta-
bilized by encapsulation with the protein zein.136) Neem
extracts are available commercially. Polygodial has
marked antifeedant activity against insects and fish. Its en-
vironmental stability is not very good. It has a very hot taste
to humans.137 The optical isomer where the aldehyde group
has the opposite configuration is tasteless. Other an-
tifeedants, such as quinine, taste bitter to humans. Whether
330
11.23
or not other species perceive these in the same way is un-
certain. Numerous analogues have been made in the hope
of remedying some of the deficiencies, enhancing activity
and obtaining a compound that can be made economically
on a commercial scale.
Numerous other insect antifeedants have been isolated
from a variety of sources. One way to search for these is
to look for a plant that would appear to be good food for
nearby insects, but that is not eaten. Two compounds that
are about as effective as azadirachtin are shown in
11.23.138 Mycotoxins can be as effective as azadirachtin
in some cases, as in the following example (11.24).139 It
would be instructive to try this technique on some of the
highly invasive exotic weeds found in the eastern United
States. It is possible that weeds such as kudzu, Lonicera
japonica, Alliaria petiolata, and Celastrus orbiculatus,
contain antifeedants that might be used on crops in the
area where they are pests. Their harvest for this purpose
11.24
Chapter 11
might help contain their spread and preserve natural bio-
diversity.
Most antifeedants are not as active as the available pes-
ticides, so that they would have to be used at higher levels.
They would work best if they were systemic to protect the
growing tip of the plant. The supply from natural sources
might not be large enough for crop use in many cases. The
antifeedant derived from betulin from the bark of birch
trees (Betula papyrifera,) shown in 11.25 is potentially
available in large supply.140
Another approach is to breed plants with large amounts
of antifeedant in them. Breeders have succeeded in pro-
ducing cotton containing high levels of gossypol in the
leaves but not in the seeds.141 This deters the tobacco bud-
worm (Heliothis virescens) while still allowing the seeds to
be used as a source of edible cottonseed oil.
Marine organisms contain a variety of antifeedants that
protect them from fish, sea urchins, and such. (Some are
11.25
Agrochemicals
11.26
also active against insects.142) Three are shown in 11.26.
The first is from a gastropod,143 the second from a nudi-
branch,144 and the third from bryozoan.145
The observation that birds do not eat Concord grapes led
to the isolation of methyl anthranilate (11.27), which is
now used to keep gulls off airports and Canada geese off of
lawns.146 Before this use, 15,000 gulls had to be shot in
1991 at John F. Kennedy Airport in New York City.
4. Pheromones
The lives of insects depend on chemical cues that are used
to locate food,147 a mate, a place to lay eggs, and other
activities. Those produced by the insect are called
pheromones.148 There are alarm, aggregation,149 sex150 and
11.27
331
other pheromones. Such chemical cues can be used to con-
trol insect populations by luring them to traps or causing
them to be repelled from the crop. Putting the chemicals of
the host plant that enable the insect to find it, the trail
pheromone, the sex pheromone, or the aggregation
pheromone in the trap can capture the insects. Putting these
same chemicals in many places other than the crop can con-
fuse the insects and disrupt their normal processes.151 This
technique of mating disruption with sex pheromones is
used to control cotton bollworms, codling moths on apples
and pears, and other insects. About 70% of Brazil’s tomato
crop is sprayed with a chemical insecticide every year to
control a caterpillar pest. The sex pheromone of the moth,
Scrobipalpuloides absoluta, has been identified (11.28)
and used very effectively to trap the male moths.152 Its gen-
eral use may be able to eliminate 90% of the spraying. This
method is species-specific; hence, it will not harm nontar-
get organisms.
A few examples of pheromones will be shown to indi-
cate the diversity of chemical structures. Many sex
pheromones of Lepidoptera tend to be long-chain aliphatic
aldehydes, acetates, or alcohols. The sex pheromone of a
rice borer is Z-11-hexadecenal (11.29).153 The sex
pheromone of the Israeli pine blast scale is shown in
11.30.154
332
11.28
11.29
Almost all the sex pheromones are mixtures. They have
to be to be enough for the thousands of insect species. The
mixture used to disrupt the mating of the codling moth con-
sists principally of (E,E)-8, 10-dodecadien-1-ol, with mi-
nor amounts of dodecan-1-ol, (E)-9-dodecen-1-ol, and
tetradecan-1-ol (11.31).155
Mating has also been disrupted by analogues, in which
a cyclopropene group has been used in place of the double
bond (11.32), in the natural sex pheromone156 (e.g., for the
female house fly).
There are also many other types of compounds (11.33)
used by insects other than Lepidoptera as sex pheromones.
The methyl esters of L-valine and L-isoleucine are used by
the cranberry white grub,157 periplanone B by cockroaches,
ipsdienol by bark beetles,158 and olean by the olive fruit
fly.159 The isocoumarin is part of trail pheromone of the
ant, Lasius fuliginosus.160
11.30
11.31
Chapter 11
The sugarcane rootstalk borer weevil is attracted to ag-
gregate by food, others of its kind, and by their frass.161 If
the pheromones involved can be identified, they can be
used in traps. Insects interact with the terpenes in plants in
a variety of ways.162 The insect may find the host plant in
this way, either to eat it, or to lay eggs in it. Terpenes such
as pulegone (11.34),163 thujone, camphor, and citronellal
repel insects (11.35). Linalool has been used as an insecti-
cide on house plants.
Blends of oils from cloves, eucalyptus, lemon grass, cin-
namon, and others that block the insect neurotransmitter
octopamine are now available commercially for use as in-
secticides.164
Because these are relatively volatile compounds, their
use as lures may require slow-release formulations that
would release the proper amount of terpene as a function of
time. Such formulations are used with the sex pheromone
11.32
Agrochemicals 333

11.33

traps. Sometimes it is as simple as impregnating a piece of

fiberboard with the liquid. Sex pheromones have also been
incorporated in plasticized polyvinyl chloride and in lami-
nated polymer films.165
Dioryctria abietivorella oviposits on white pine in re-
sponse to volatile emissions of myrcene and 3-carene
(11.36).166 Terpenes can both deter and stimulate oviposi-
tion of the European corn borer. In a series that was
screened, the best deterrent was farnesal and the best stim-
11.34 ulant -humulene (11.37).167

11.35
334 Chapter 11

11.38

molting hormone. Insects can be destroyed by preventing

11.36 them from molting or causing them to molt prematurely.
Some plants use a defense of making phytoecdysteroids to
interfere with insect growth regulation. Ajuga reptans does
An egg parasitoid uses the sex pheromone of the tussock
this.172 Four phytoecdysteroids (11.41)—20-hydrox-
moth to find the eggs, which are deposited shortly after
yecdysone, norcyasterone, cyasterone, and isocyas-
mating.168 An oviposition attractant for the mosquito,
terone—are produced at 0.5% in hairy root cultures.173
Culex pipiens fatigans, is shown (11.38).169
Neotenin (11.42) is an insect juvenile hormone.174 The
The use of such materials to induce the mosquitoes to
level of juvenile hormone must drop for metamorphosis to
lay eggs in locations unsuitable for their development
take place. A carbamate (11.43) causes fatal morphological
could reduce the amount of pesticide needed to control
changes in the insect if applied when the inherent juvenile
populations. The European cherry fruit fly lays only one
hormone is low.175 It is nontoxic to warm-blooded animals
egg in a cherry, then marks the cherry with an ovipositing
and fish. It could still be toxic to many beneficial insects.
deterrent (11.39).170 Spraying the tree with this deterrent
Rohm and Haas has devised diacylhydrazine agonists of
reduced the infestation dramatically.
ecdysone (11.44) for caterpillar control that induce a pre-
The bark from pines infested with the southern pine bee-
mature lethal molt in a few hours.176 It does not harm ben-
tle attracts two species of parasitoids.171 If the compounds
eficial insects, such as bees, ladybugs, and wasps. How-
involved can be identified, they might be put on the pine
ever, it could be toxic to other butterflies and moths, at least
trees at the first sign of a beetle. It might be necessary to
some of which are natural pollinators.
augment the supply of parasitoids by releasing some reared
Fleas on animals can be controlled by methoprene
in the laboratory.
(11.45), a juvenile hormone mimic that prevents the con-
In some insects, a male marks the female after mating so
version of larvae into pupae.177 Another chemical,
that she will not mate again. If this pheromone can be used
lufenuron (11.46) is given to the animal orally. Any flea that
on the females before any male arrives, any eggs laid will
bites the animal becomes sterile by inhibition of the devel-
be sterile.
opment of chitin, a vital polymer in the exoskeleton. These
chemicals should have minimal effects on other species.
5. Insect Growth Regulators
The prothoracicotropic hormones that activate the syn-
Insects have exoskeletons. To grow, they must molt. This thesis of ecdysone in Lepidoptera are highly species-spe-
process is controlled by 20-hydroxyecdysone (11.40) a cific, unlike other insect neuropeptides. If something can

11.37
Agrochemicals 335

11.39

11.40

11.41

11.42
336 Chapter 11

11.43

11.44

11.45

be found that blocks the receptor for these hormones, it
may be a highly specific insect control agent.178
6. Phytoalexins
The coevolution of plants with the bacteria, fungi, insects,
nematodes, viruses, and others that attack them has led to
11.46
various defenses in the plants.179 Chemicals produced in
response to the attack are called phytoalexins. They in-
clude poisons, feeding deterrents, proteins that block the
insect’s digestive enzymes (such as protease inhibitors),
chitinase (for destroying the fungal cell wall or the
insect’s exoskeleton), enzymes for the production of
callose to wall off the area of attack, volatile compounds
that attract parasitoids to the insect, phytoecdysteroids
to interfere with molting, accumulation of phenols, and
other mechanisms. In some cases, the response is sys-
temic and protects the plant for days. Localized cell and
tissue death at the site of infection may deter the en-
emy.180 Insects may, in turn, detoxify, sequester, or by-
pass these defenses. When the beet army worm feeds on
maize seedlings, volicitin (11.47) in the worm’s oral se-
cretions causes the plant to produce volatile compounds,
Agrochemicals 337

11.47

such as terpenes, that attract wasps that parasitize the

worm.181
Jasmonic acid (also derived by biosynthesis from 18-
carbon unsaturated fatty acids; 11.48) is often involved in
the signaling in the plant to respond to the threat.182
Salicylic acid 11.49 is another signaling molecule in the
plant’s response. The amount of jasmonic acid rises in 5
min after the insect begins feeding on the tobacco plant.
The acid reaches the roots in 2 h and a flush of nicotine 11.50
reaches the leaves (up to 120 mg/g leaf) in 7 h. Both of
these acids can trigger the release of volatile compounds
cosidase when the plant is attacked.185 These resist insect
from the plant. These include not only terpenes, but also
and microbial attacks.
methyl jasmonate and methyl salicylate, which can signal
It may be possible to protect plants by treating them
nearby plants to mount their defenses against attack.183
with elicitors that cause the synthesis of phytoalexins be-
Methyl jasmonate also inhibits the sprouting of potatoes.184
fore there are very many insects or disease organisms
Cyclic hydroxamic acids (11.50) stored in corn and
around.186 Chitosan from the deacetylation of chitin (an
wheat seedlings as their glucosides are released by a glu-
acetylated polymer from glucosamine found in crab shells,
fungi, and insect exoskeletons) can elicit such a response.
So can oligogalacturonides (degree of polymerization
8–15). Fungal endogalacturonases cause the release of such
oligomers from pectin in plant cell walls in 15 min. Hydro-
gen peroxide, as such, or in some slow-release bound form,
might be a suitable elicitor for sweet potatoes, beans, and
sugar beets, where attack by Fusarium fungi produces hy-
drogen peroxide that stimulates the production of phy-
toalexins.187 Aluminum chloride has been shown to be an
11.48 elicitor for resveratrol (11.51) in grapevines.188

11.49 11.51
338 Chapter 11

This phytoalexin helps the plant resist attack by gray

mold (Botrytis cinerea). Another possibility is to use a phy-
toalexin made by a chemical synthesis apart from the plant.
Novartis sells a benzothiadiazole (Actigard) that elicits
systemic resistance to bacterial and fungal pathogens.189

7. Miscellaneous Methods of Insect Control

Fumigants are used to kill organisms in the soil, in stored
fruits, and grains, houses, libraries, and so on. The debate
about the use of methyl bromide, which can cause ozone
depletion in the stratosphere, was described in Chap. 3.
Methyl iodide has been proposed as a replacement because
it photolyzes in the troposphere and is unlikely to cause
ozone depletion.190 However, it is a highly toxic cancer-
suspect agent. Chopped broccoli has been worked into the
soil before planting cauliflower to eliminate a wilt caused
by Verticillium dahliae.191 This replaced methyl bromide.
11.53
Irradiation of food can be used to replace fumigation for in-
sects.192 It has been used on spices, strawberries, tomatoes,
grapefruit, poultry, and others. Chilling fruits to 34°F (1°C) Flies that have translucent guts can be killed by eating
or less for 12 days will kill fly eggs and maggots.193 Forc- dyes that will form singlet oxygen in the light.200 Phloxine
ing hot air through papayas and citrus eliminates fruit B (11.53) and uranine (11.54) are suitable dyes. They are
flies.194 used in food and cosmetics. When these two were ingested
Repellents such as azadirachtin and the repellent in by fruit flies, followed by light, there was 100% mortality
11.52 can be used to keep insects out of stored grain.195 in 2–12 h. The method is suitable for use with pheromone
The pirate bug has been used to control insects such as traps that may or may not contain an insecticide. Some
the Indian meal moth in stored grain.196 Stored grain can traps contain sticky panels for the insects. Others just have
also be protected from insects by an atmosphere of carbon a transparent trap with a small hole that the insects can get
dioxide.197 Insects in library and museum materials can be into but cannot seem to figure out how to get out. This is an
killed by keeping the materials under nitrogen for 8–10 alternative to phosphorothioate insecticides, such as
days.198 Another method is to heat to 140°F (60°C) for malathion. Because no light enters the guts of mammals,
2–4h. Freezing to 20 to 40°C. works if the temperature birds, and fish, they are unaffected by such treatments. As
is reduced within 24 h. more than 100 photosensitizers have been isolated from
Cockroaches can be eliminated from homes by putting higher plants, this may be another mode of natural plant
boric acid or silica gel in cracks and other places where defense.
they may live.199 These materials are thought to work by
destruction of the waxy coating on the insect’s body. They
may also be ingested by grooming.

11.52 11.54
Agrochemicals
Soft-bodied insects, such as aphids, can often be con-
trolled by relatively pure soaps of fatty acids. Acid mine
drainage involves the oxidation of pyrite and other metal
sulfides by Thiobacillus ferrooxidans. It can be controlled
by detergents that wash away the surface fatty film on the
bacteria that normally protects them from the acid.201 The
glycolipids on the surface of the leaves of petunias have in-
secticidal properties. The preparation of analogues has
shown the diheptanoyl and dioctanoyl esters of sucrose to
be potent insecticides for tobacco aphids and sweet potato
white flies.202 Sugar esters extracted from Nicotianum
glutinosa controlled white flies.203 (These glycolipids
break down the outer coating of soft-bodied insects, but are
relatively nontoxic to hard-bodied insects, such as lady
beetles.) Soft-bodied insects can also be controlled by ap-
plying horticultural oils (clean petroleum fractions), either
during the growing season or in the off season.204
B. Weed Control
1. Mechanical and Cultural Methods
Before the advent of herbicides, weeds were removed by
mechanical cultivation. Herbicides were adopted because
they made weeding cheaper without any mechanical dam-
age to the crop. Both methods involve more erosion of soil
than is desirable. There are some other ways to cut down on
the crop losses to weeds.205
The seeds of the crop should be as free of weed seeds as
possible. Proper composting of animal wastes before their
use as fertilizer will involve a temperature high enough to
kill any weed seeds present. Weeds are primarily pioneer
plants of disturbed habitats. The seeds can remain dormant
in the soil seed bank for many years. The seed germination
is triggered by more than a minimal diurnal variation of
temperature, or in some cases by light. In Iowa, tillage at
night reduced the incidence of weeds by 50% or more.206 If
a no-till system, with a relatively harmless herbicide such
as glyphosate, is used, the seeds will not be brought to the
surface and will be less likely to germinate. For those that
do germinate, a second pass with glyphosate can be used.
(Although glyphosate207 is relatively harmless, it is made
with hydrogen cyanide, which is very toxic.) Monsanto has
developed a process (11.1) for making the intermediate
iminodiacetic acid, which eliminates the need for the
NaOH
NH3  2 HCHO  2 HCN N HN(CH2CN)2
O2
Raney copper
HN(CH2CH2OH)2
339
HCN,208 but is building new plants based on both routes.209
Even the new route is not free of toxic chemicals, because
the diethanolamine is made by reacting the carcinogen
ethylene oxide with ammonia.)
Ridge tillage uses an herbicide only under the 6- to 8-
in.–high ridge that serves as the seedbed for the crop.210
The ridge is warmer so that the seed germinates before any
seeds between the rows. Use of a string trimmer for the
weeds that did develop between the rows gave a system
that reduced herbicide use by 60% over conventional
spraying.211 The fertilizer is applied to the ridge with the
first cultivation, the amount being limited to what the crop
can actually use. Putting the fertilizer in a narrow subsur-
face band under the seed with conservation tillage is better
than broadcasting the fertilizer.212 These methods reduce
soil loss by 90% over that in a plowed field. If the weeds
between the rows are mown, less soil will be lost than if the
soil is actually disturbed to take out the weeds.
Small succulent weeds between rows of taller woodier
plants can be removed with a tractor-drawn flamer. The
aim is not to burn up the weeds but just to achieve cell rup-
ture. This method has been used to weed alfalfa, maize, cot-
ton, sugarcane, and soybeans. High technology sprayers
that determine the precise locations of weeds in soybeans
by light and computer chips have been used to reduce the
amount of herbicide needed by using only short bursts to
spray the weeds.213 If this technique can be adapted to
flame spraying or to the use of mechanical cutters, the her-
bicide can be eliminated.
Planting crops in narrow rows (0.25–0.38 m) can help
suppress weeds by shading them.214 When this was used,
with some cultivation, soybean and sunflower yields did
not go down. Maize yields were 10% less than in conven-
tional practice with herbicides. Weed grasses in wheat
were reduced by a combination of seeding 50% more per
acre, choosing a taller wheat variety, and applying the fer-
tilizer 5 months before planting so that the deeper roots
(versus the weed grasses) of the wheat reached it first.215
Crop rotation also helps, because some weeds tend to asso-
ciate with certain crops. Intercropping can suppress
weeds.216 Intercropping maize and velvet beans has
worked well in Honduras. This has doubled or tripled the
yield of maize. Legumes are often used as cover crops,
which may not be harvested.217 This living mulch reduces
HN(CH2COONa)2 N (HO)2P(O)CH2N(CH2COOH)2
NaOH
97% yield
(HO)2P(O)CH2NHCH2COOH
(11.1)
340 Chapter 11

soil erosion, suppresses weeds and puts nitrogen into the

soil, so that less or no nitrogen fertilizer has to be added.218
Weed suppression is best if the cover crop is also mown. In
one form of conservation tillage, a tall forage soybean was
grown and cut, after which broccoli seedlings were planted.
This method cut chemical use in half.219 Nonliving
mulches can also suppress weeds. They are used with
strawberries, pineapples, sugarcane, and some vegetables.
They are very common in home landscaping. Crop residues
can often be used as mulches. For a sustainable agriculture,
it would be better not to use a plastic derived from 11.55
petroleum as a mulch.

2. Predators and Pathogens for Weed Control
Chickens and geese have been used to remove weeds from
an apple orchard intercropped with potatoes.220 This does
require frequent moving of the animals and the fences used
to contain them. Sterile grass carp have been used to re-
move aquatic weeds.221 Many of the worst weeds have
been imported from other parts of the world without their
natural enemies. In these cases, biological control can be
very effective, if one is absolutely certain that control
agents are species-specific and will not shift to other hosts.
Meeting this requirement means that finding a suitable con-
trol agent may take quite a bit of time. An example is the
use of a moth and weevils for water hyacinth, which is a
problem in the southeastern United States.222 The larvae of
the soybean looper have been used to control kudzu in
North Carolina.223 Each larva is injected with the egg of a
stingless wasp which kills the looper before it becomes a
moth. The egg makes the larva eat at 1.5 times the normal
rate.
Fungal pathogens can also be useful in controlling other
weeds.224 Colletotrichum gloeosporioides controls north-
ern joint vetch. Phytophora palmivora has been used to
control strangler vine in citrus groves. Puccinia canalicu-
lata is registered for control of a sedge, Cyperus esculenta.
Colletotrichum truncatum is effective on hemp sesbania, a
common weed in cotton and soybean fields.225 The bac-
terium Xanthomonas campestris can control Poa annua in
turf, but the treatment is slow, requiring 50–60 days.226
Velvetleaf can be controlled in this way.227 The insect that
feeds on the seeds can spread the fungi. Thus, it is possible
to use native fungi which are simply applied at higher lev-
els when needed. These need to be easy to grow in quantity
and to remain viable after prolonged storage. The right for-
mulation can enhance activity and improve consistency of
treatment. They need to be safe for nontarget organisms.
It is also possible to use toxins isolated from fungi. The
cyclic tetrapeptide, tentoxin, from Alternaria species
causes severe chlorosis in many problem weeds without
hurting maize or soybeans.228 Another cyclic peptide
(11.55) from Alternaria alternata kills the weed, Centau-
rea maculosa.229 The toxin is host-specific.
3. Allelopathy
Many plants elaborate chemicals (allelochemicals) that in-
terfere with the growth of others around them.230 The black
walnut tree is an example. It is possible for some of these
materials to be of use in controlling weeds. (Intercropping
the allelopathic species with a tolerant crop is a possibility
for weed control.) A plant growth inhibitor (11.56) from
Ailanthus altissima inhibits the growth of several weeds.231
(This tree is a weed in the eastern United States.) The
volatiles from defatted seed meal of Brassica napus reduced
the germination of lettuce seed from 95 to 10–15%.232 Per-
haps, the meal could be applied to a field to inhibit germi-
nation of weeds. An allelopathic substance from the rhi-
zomes of Elymus repens inhibited the germination of alfalfa
at a concentration of 106 g/mL.233 A root culture of Menis-
permum dauricum produced germination stimulants234 for
Striga hermonthica, a root parasite weed.235 Such stimu-
lants might be used to cause the weed seed to germinate in
the absence of the crop, so that the seedlings would die out.
Many germination stimulants are not very stable in the field.
11.56
Agrochemicals
11.57
Perhaps, they can be stabilized with antioxidants, light sta-
bilizers, encapsulation, and such.
Antibiotics can also be used for weed control. Monsanto
isolated one from a Streptomyces culture (11.57) that
showed over 90% phytotoxicity to several broad-leaved
weeds, without hurting wheat at a level of 7 g/acre.236
4. Killing Weeds with Light
Porphyrins are formed biosynthetically from -aminole-
vulinic acid (11.58). Application of this material can lead
to porphyrins in the dark. When the plant is exposed to
light, the excess porphyrins produce singlet oxygen that
kills the tissues.237 This method has some problems besides
having to spray in the dark. There is no cheap synthesis for
the compound that gives high yields. This may change now
that a method for converting waste paper to levulinic acid
in 70% yield has been developed.238 It has also been made
by microorganisms.239 The culture broth killed several di-
cotyledonous weeds. This may be cheap enough for com-
mercial use. (-Aminolevulinic acid and various por-
phyrins have also been used with light in the treatment of
skin diseases.240)
C. Control of Plant and Animal Pathogens
It is important to be able to control plant diseases caused by
bacteria, fungi, and viruses in an environmentally sound
way,241 insofar as possible without the use of chemical pes-
ticides. The classic method has been to breed resistant
crops using genetic material from resistant wild relatives.
11.58
341
Now that the molecular genetics of plant disease resistance
is starting to be understood and disease resistance genes
characterized,242 it may be possible to use genetic engi-
neering to develop resistant cultivars more quickly. The
problem is that some breeders stopped breeding for disease
resistance because they felt that cheap chemicals would
take care of the disease. They are beginning to breed for re-
sistance again now that blights have developed that chem-
ical fungicides cannot handle. “Because late blight (of
potatoes) had been controlled with chemicals since the
middle of the 20th century, breeding for resistance to the
disease was not a top priority in the United States.”243 An
alternative program for control of fungal diseases of wheat
and barley in the Pacific Northwest of the United States in-
volves the use of resistant cultivars, seed treatments with
fungicides, and planting dates that are least favorable for
infection.244 For root pathogens, crop rotations with non-
host crops can also help.
There is an effort to exploit microbe–microbe interac-
tions to control plant pathogens.245 The beneficial mi-
crobes may control the pathogens in a variety of ways.246
These include competition for living space, competition for
key nutrients, production of siderophores that capture nu-
trient metal ions more effectively, production of plant hor-
mones, induction of resistance mechanisms in the host,
production of antimicrobial substances, making cell wall
degrading enzymes, and so on. Genetic engineering is be-
ing used in an effort to improve these beneficial mi-
crobes.247 The problems in the use of the beneficial
microbes involve finding inexpensive methods of produc-
tion248 and storage as well as obtaining consistent results
under field conditions. The latter means that the variables
involved need to be better undertood. The storage stability
of beneficial fungi and bacteria has been improved to 6
weeks to 6 months at room temperature, and 2 years in the
refrigerator, by adding a sugar to stabilize cell mem-
branes.249 Some biocontrol methods work better in green-
houses than in open fields simply because the environment
in the greenhouse is easier to control. A few of the more
promising examples will be given.
342
Pseudomonas fluorescens controls fire blight by out-
competing with it for nutrients.250 The soil fungus Tri-
choderma sp. controls late blight of potatoes caused by
another fungus, Phytophora infestans, as well as some
species of Pythium that cause damping off (a fungal dis-
ease).251 The Trichoderma can be applied as a seed treat-
ment. Another soil fungus, Gliocladium virens, controls
damping off caused by Pythium ultimum and Rhizoctonia
solani. Both of these beneficial fungi can be grown in fer-
menters. Seed treatment with a mixture of bacteria, En-
terobacter cloacae and Burkholderia cepacia, prevented
damping off caused by Pythium and Fusarium species.252
The use of a methyl cellulose coating improves some of
these seed treatments.253 Fusarium wilt has also been pre-
vented by mix cropping Allium fistulosum with bottle
gourd to provide the Pseudomonas bacterium which con-
trolled the Fusarium.254
The fungus Ampelomyces quisqualis is marketed for the
control of powdery mildew on grapes.255 Mild strains of
bacteria, fungi, and viruses can prevent disease by outcom-
peting more virulent strains.256 A mild strain of a citrus
virus is used in Brazil for this purpose.257 This method is
also used to prevent chestnut blight in Europe.258 The
American chestnuts were one-third of the trees of the
oak–hickory–chestnut association in the eastern United
States until an imported blight wiped them out, except for
a few stump sprouts. The challenge is to find enough strains
of the hypovirulent fungus to reintroduce the chestnut.
Lactobacillus bacteria can destroy gut pathogens in
farm animals for faster growth.259 This offers an alternative
to the use of antibiotics. A mixture of 29 types of live bac-
teria is being marketed for the elimination of Salmonella
from chickens.260 These are sprayed as a mist over newly
hatched chicks. A brief burst of 290°F steam kills
Salmonella on chickens.261 This is an alternative to irradi-
ation or treatment with bactericides.
Postharvest diseases can also be controlled with other
organisms.262 Naturally occurring Pseudomonas bacteria
can control rotting of apples, citrus, and pears while they
are in storage.263 One possibility is to put the bacteria in a
fruit coating. Molding of kiwi fruit by Botrytis can be con-
trolled by an extract of Trichoderma fungus which contains
6-pentyl--pyrone (11.59).264 It is also effective against
several fungi. Because it is expensive to make chemically,
its growth on moistened ground maize is being studied, but
yields are still low at 2 g/kg.265
The essential oil of Salvia fructicosa, which contains the
terpenes 1,8-cineole, - and -thujone, and camphor, kills
herpes simplex virus and several strains of bacteria.266 An-
timicrobial peptides of plants and animals267 that resist in-
fection of the host can now be produced in recombinant
bacteria.268
Chapter 11
11.59
Many fungicides are being isolated from a variety of
natural sources. Some of them may be useful as such. More
often, variations on their structure are made to enhance ac-
tivity; reduce toxicity to the crop plant; increase their sta-
bility to hydrolysis, light, enzymes; and to make their
chemical syntheses commercially attractive. Strobilurin
(11.60) is such a case. It was isolated from a wood-rotting
mushroom. This lead has resulted in a whole new class of
fungicides, the -methoxyacrylates.269 A related com-
pound is found in another mushroom.
A variety of other fungicides with many different types
of structures are being isolated from natural sources. Some
of the structures are simple enough so that analogues could
be made relatively easily. Others are complicated enough
that total synthesis would be impractical on a commercial
scale. In such cases, the hope is that simpler analogues of
part of the structure will be active. If not, the material will
have to be isolated from natural sources, perhaps with some
synthetic modification later. Microorganisms can often be
grown in large fermenters, providing that a proper medium
can be found.
A few examples can illustrate the wide diversity of ac-
tive compounds. An antibiotic from a culture of Strepto-
myces flaveus (11.61) showed strong activity against four
fungi with little toxicity to the host plants.270 Polycyclo-
propanes (11.62) from Streptomyces fermentation broths
are active against filamentous fungi.271 A diketone (11.63),
from the fungus Trichoderma viride is a fungal growth in-
hibitor for the biocontrol of soil-borne pathogens.272
The rice blast fungus, Magnaporthe grisea, uses a
special cell for pathogenesis. A polypeptide from the
yeast, Saccharomyces cerevisiae, blocks the formation of
this cell and prevents infection by some strains of the
fungus.273 The authors plan to make a variety of ana-
logues, perhaps by combinatorial chemistry, to test on
this and other strains. Germinating seeds can produce
compounds that protect the seeds from pathogens.
Malted barley is active against plant pathogenic fungi
and bacteria.274 This should be much less expensive and
easier to produce than many of the other compounds
mentioned in the foregoing.
The wood (Thuja dolabrata) in a 1200-year-old pagoda
in Japan shows no signs of rot or termites.275 The most ac-
Agrochemicals 343

11.60

pregnated with a monomer derived from carvacrol that

might then be polymerized in the wood by heat or irradia-
tion. An acrylate from carvacrol is one possibility. An al-
ternative would be to make such a polymer, then impreg-
nate the wood with it. The idea is to obtain slow release by

11.61

tive compound in the wood against such invading organ-

isms is carvacrol (11.64).
It is possible that this or a similar compound could be
used to replace the copper–chromium arsenate treatment
now used on wood. Carvacrol is fairly volatile, bp 237°C.
It would be interesting to see how fast it would be released
from wood treated with it under pressure. If it is released
too fast for purposes of preservation, the wood could be im- 11.63

11.62
344
11.64
hydrolysis or by some action of the invading organism. An-
other possibility would be to use a carvacrol-impermeable
sealer on the impregnated wood. A disadvantage is that any
new surface, such as a saw cut, might have to be sealed
anew. If wood preservatives are considered as pesticides,
they are more than one-third of the total used.276 The use of
steel or concrete utility poles has been suggested as a way
of reducing this usage.
D. Fertilizers
There is a global nitrogen overload resulting from fertilizer
use, fossil fuel emissions, and the growing of nitrogen-fix-
ing crops, such as soybeans.277 The world uses more than
280 million lb of fertilizer each year, with maize taking the
most, followed by wheat and soybeans.278 About 20% of
this leaves the watershed in the rivers. To this must be
added the nitrogen and phosphorus that wash off or leach
through the soil when animal waste is applied to the land in
amounts too large for the crop to assimilate. (Sixteen per-
cent of the counties in the United States produce more ma-
nure than the crops can use.279) For example, the nitrogen
input to the Baltic Sea has quadrupled since 1900. The re-
sult has been algal blooms with subsequent dead zones in
coastal areas worldwide, including the Adriatic, Baltic, and
Mediterrean Seas, Hong Kong, Japan, the Gulf of Mexico,
and Chesapeake Bay in the United States. The third largest,
the one in the Gulf of Mexico, is the size of the state of New
Jersey and is due to the 1.8 million metric tons of nitrogen
that comes down the Mississippi River each year, three
times the amount that came down 40 years ago.
Experiments with irrigated wheat in Mexico demon-
strated that with less fertilizer and better timing (one-third
at the time of planting and two-thirds 6 weeks later, the
yield and quality was just as substantial and after-tax prof-
its were 12–17% more.280 The use of legumes as cover
crops and intercrops to put nitrogen into the soil was dis-
cussed earlier. If practiced widely, this would greatly re-
duce the need for synthetic nitrogenous fertilizers. The ex-
ample of intercropping beans and maize in Honduras that
Chapter 11
was mentioned earlier is especially instructive because
maize accounts for about 45% of fertilizer consumption in
the United States.281 In some cases innoculation of the
legumes with nitrogen-fixing bacteria can help.282 The re-
cycling of all organic materials on the farm will help pre-
vent loss of nutrients. It will also help cut erosion and soil
loss. Phosphorus is often lost with the soil that is lost by soil
erosion. Municipal organic wastes, including treated
sewage sludge, as well as agricultural wastes, can also be
used to build up the organic matter in the soil and add nu-
trients to it.283 More than 8000 farms in the United States
are now composting dead animals, manure, and crop
residues.284 This also increases the water infiltration rate
and water-holding capacity of the soil. As long as chemical
insecticides that harm them are not applied, Lumbricus ter-
restris earthworms can help incorporate the organic matter
into the soil.285 The worms feed by dragging surface mat-
ter into their burrows where nitrogen compounds can be re-
leased into the soil. Water infiltration, root penetration, and
air exchange are also helped by this process.
Outbreaks of the microorganism, Pfiesteria piscicida, in
Maryland and North Carolina, which caused fish kills and
some human illness, have been linked to the nutrient pollu-
tion from hog and chicken farms, municipal sewage, and
aquaculture impoundments.286 Several states have enacted
legislation to control pollution from animal waste and more
has been proposed for the 450,000 feed lots in the United
States.287 The Netherlands has the most comprehensive
legislation of this type. The main barrier to the wider use of
such wastes, as well as composted waste of swine and
chickens, is the cost of transportation. This, apparently, is
not a problem in the home-gardening market. Composted
sewage sludge from Milwaukee, Wisconsin (Milorganite)
and composted cow manure from Vermont (Moo Doo) are
available in a local gardening store in Newark, Delaware.
Other uses that are technically feasible, but may not be eco-
nomic unless a dollar value is assigned to the harm caused
by the nutrient pollution, include combustion to produce
electricity, production of biogas, duckweed, single-cell
protein, and mushrooms.288 Biogas produced from poultry
waste could be used to heat and cool the chicken houses.
Duckweed, single-cell protein, and fly maggots raised on
the waste could be fed back to the chickens. The use of low
phytate corn or adding phytase to the feed can reduce the
phosphorus in the waste by about 38%.289 The use of alu-
minum sulfate to reduce the phosphorus runoff from the
land by 70%290 may result in an undesirable buildup of
aluminum and acidification of the soil.
Composted rock phosphate is said to be as good as su-
perphosphate.291 This avoids the need for sulfuric acid in
making phosphate fertilizer. The need for phosphate fertil-
izers can be reduced by the use of symbiotic fungi (mycor-
Agrochemicals
rhizae) that live in or attached to the roots of plants. They
are essential for good growth of many native trees and
herbaceous plants. It may be helpful to use them more on
crop plants. They will grow as long as no fungicides are ap-
plied to the crop. Among the companies selling them is
Plant Health Care of Pittsburgh, Pennsylvania. The hunt for
improved strains is ongoing.
A different approach to using less fertilizer and fewer
pesticides is to shift to different crops. Industrial hemp re-
quires no pesticides and little fertilizer compared with cot-
ton, which is typically grown with lots of pesticides.292 “If
you smoke industrial hemp, all you’ll get is a headache.”
Hemp fiber has been used to make cloth for hundreds of
years.
IV. LAWNS
Lawns are given a special place in this discussion because
of the many problems associated with their ubiquitous use.
Lawns have come into widespread acceptance since the
invention of the lawn mower in 1830.293 They require
about 27,000 gal of water per acre each week to keep them
green in the summer. This use of water could be avoided if
the exotic cool season grasses that make up the lawn were
allowed to go dormant (and brown) as they do naturally. In
Novato, California, in water-short Marin County, just north
of San Francisco, California, where 33% of the water sup-
ply goes on to lawns, the water district will pay up to 310
dollars per home to rip out the lawn and replace it with
plants adapted to the semiarid climate.294
The average lawn receives 5–10 lb of pesticides per acre
per year. This is the heaviest pesticide application of any
land area in the United States. Of the 285 million lb of pes-
ticides used annually in the United States, 67 million lb are
applied to lawns.295 In New Jersey, more pesticides are
used on lawns and golf courses than for agriculture. 296
More than 2 million lb are applied to lawns in the state each
year. More fungicides are used on turfgrass each year in the
United States than on any other crop.297 Golf courses in
New York and Japan use seven to eight times as much pes-
ticide per acre (18 lb/yr on Long Island, New York) as
nearby agricultural land.298 (The pollution from golf
courses apparently varies with the locality and the methods
of management used, being higher than agricultural land in
some cases,299 and lower in others.300 )
There are 61 million lawn mowers in the United States,
most of them powered by gasoline.301 For a unit of fuel,
they emit 50 times as much air pollution as an automobile.
Very few people use hand-powered mowers, which cause
little or no air and noise pollution. Municipal solid waste
contains about 18% of yard waste (see Chap. 14). In the
345
summer, most of this consists of grass clippings and, in the
fall, leaves raked off of the lawn to keep the grass from
smothering. It is better to let the clippings stay on the lawn
and to put the leaves in a compost pile, either in the back
yard, a neighborhood pile, or a town pile. The nutrients can
then be reused. A modified gibberellin has been found that
reduces the growth of grass by threefold, so that mowing
can be less frequent.302 It is not yet on the market.
In 1995 a popular four-step lawn care program from
Scott used the following:
Step 1: 1.51 lb/acre of preemergence herbicide (pen-
dimethalin)
Step 2: herbicides for broad-leaved plants (1.51 lb/acre
2,4-dichlorophenoxyacetic acid plus) (1.51 lb/acre
2(2-methyl-4-chlorophenoxy)propionic acid).
Step 3: 0.461 lb/acre insecticide (diazinon)
Step 4: no pesticide
Each step included fertilizer (30-3-10 in step1, 32-4-3 in
step 2, 28-6-4 in step 3, 32-3-10 in step 4 [at 123
lb/acre]). The numbers refer to the amounts of nitrogen,
phosphorus, and potassium in the fertilizers.) Part of the
nitrogen in the fertilizer was available to plants immedi-
ately (ammonium dihydrogenphosphate) and part after
slow release (urea plus urea–formaldehyde reaction prod-
ucts). The high nitrogen content of the fertilizer makes the
grass grow rapidly and would not be used on an agricul-
tural crop. The use of clover in lawns to fix nitrogen was
common until, as one author puts it, a turf company de-
clared clover to be a weed and sold a chemical to kill it.303
Lawns of bent, foxtail, and fescue grasses need less potas-
sium and have fewer dandelions, because both the dande-
lions and Kentucky blue grass require relatively large
amounts of potassium.304 (Efforts are underway to see if
this principle can be applied to weeds in other crops.)
Scott also markets moss control granules for lawns con-
taining a mixture of iron(II), magnesium, and potassium
sulfates to be applied at 122 lb/acre. Diazinon is a
cholinesterase inhibitor that is toxic to birds and earth-
worms. As a result of a number of bird killings, its use on
golf courses has been banned.
The biggest problem is that the materials applied to the
lawn do not necessarily stay there when it rains or the lawn
is overwatered. They can go into groundwater or into
streams. The result can be loss of aquatic vegetation and
animal life in streams and lakes from the herbicides and in-
secticides, as well as eutrophication, which often involves
growth of undesirable species, from the fertilizer. The re-
sult may well be a loss in biodiversity. Biodiversity can
also be lost if native wild flowers and shrubs are replaced
by lawn, as often happens. (The lawn is a biological desert
of a few species of Eurasian grasses.305)
346
Lawns prevent soil erosion, and serve as a fire break and
as a place to play. There is not much playing on lawns.
Where there are fine lawns, the children usually play on the
driveway or in the street. People usually sit on their deck
instead of on the lawn. Lawns are largely a matter of cus-
tom. Although they can be made less harmful by the meth-
ods of alternative agriculture discussed in the foregoing,
the questions should be: Are they needed? Can the same
objectives be accomplished in other less harmful ways?306
The first step is to keep the amount of lawn to a mini-
mum using species and cultivars resistant to drought and
pathogens. Alternatives to lawns include (a) ground covers,
such as species of Vinca, Pachysandra, Hedera, or others;
(b) wildflower meadows; (c) mixtures of flowering shrubs,
herbaceous perennials, and annuals with paths of gravel,
bark, brick, flagstone, or other material in them; (d) the nat-
ural leaf litter and flowers of the forest floor, (e) moss,
where applicable, and (f) xerophytic (i.e., dry) plantings of
cacti, yuccas, and such. Meadow plantings offer lower
maintenance, lower long-term costs, colorful flowers, and
a home for beneficial insects, birds, and butterflies.307 They
do not have to be watered or fertilized. Some corporations
are now using such meadows in lieu of lawns to help their
bottom lines.
V. GENETIC ENGINEERING
Genetic engineering offers great potential for improving
crops (as mentioned in Chap. 9).308 The goals include re-
sistance to drought, disease, frost, and salt; less need for
fertilizer; higher protein content; and higher levels of lim-
iting amino acids in proteins. It can often produce the de-
sired plant in less time than conventional breeding and
achieve results not available by conventional breeding,
such as producing 12-carbon fatty acid derivatives in rape.
Strategies to improve the resistance of plants to bacterial
diseases by genetic engineering include producing antibac-
terial proteins, inhibiting bacterial pathogenicity or viru-
lence factors, enhancing natural plant defenses, inducing
cell death at the site of infection, and enhancing production
of elicitors for disease response.309 Modification of the
DNA of nitrogen-fixing Rhizobium has made it more com-
petitive in nodule formation in legumes.310 However, the
major uses today of imparting resistance to insects and her-
bicides have been questioned.311
Putting foreign genes in crops can outwit insects and
fungi. Losses of stored peas to weevils have been reduced
by putting in the gene for an -amylase inhibitor from a
common bean.312 Putting a chitinase gene into rape made it
resistant to three fungal pathogens.313 Growth of insect lar-
vae was suppressed when a chitinase gene was put into rice
Chapter 11
and tobaco plants.314 Transgenic rice with an introduced
protease inhibitor from potato was resistant to the pink
stem borer.315 This inhibitor is destroyed when the potato
is cooked so that no one will eat it. Tobacco plants were
made more resistant to soil-borne fungi by the addition of
a gene for an antiviral protein from pokeweed (Phytolacca
americana).316 When mosquitoes eat Chlorella that has
been engineered to contain a gene for a mosquito digestive
control hormone that prevents the digestion of food, they
die.317 The freeze-dried alga can be stored for long periods.
Clearly, the technique works. The problem is one of the in-
vading organism developing resistance.
The most common transformation is the addition of
genes that express B. thuringiensis toxins to kill insects.
These have been put into 30 crop species, including canola,
maize, cotton, potatoes, tomatoes, and tobacco.318 Several
insect species have already developed resistance to these
toxins. It takes only a single resistance gene in the dia-
mondback moth, a major pest of cabbages and leafy
crops.319 The European maize borer has also become resis-
tant in laboratory trials.320 Monsanto’s transgenic cotton321
was used by 5700 growers on 1.8 million acres (13% of the
total cotton acreage) in 1996 and on 61% of cotton in
2000.322 It gave a 7% increase in yield. In the 40% of fields
where spraying was also needed, one spraying sufficed. By
1998, 69.5 million acres of transgenic crops were planted
worldwide.323 Insect resistance accounted for 28% of this
and herbicide resistance for 71%. Soybeans accounted for
52%, maize 30%, cotton 9%, and canola (rapeseed) 9%.
The fear is that insect resistance will develop relatively
rapidly, as it did in the diamondback moth. Then, B.
thuringiensis will no longer be available to organic farmers
as a valuable part of integrated pest management. Efforts to
prevent the development of resistance involve planting
refugia of conventional varieties.324 There is considerable
debate over how large the refugia need to be and how well
they will work. A possible way to avoid or delay resistance
has been demonstrated in tobacco. Insertion of a promoter
gene produced plants that made a toxic protein only after
the plant was sprayed with 0.1% ethanol.325
Another problem that can arise is hybridization of the
transgenic crop with wild relatives growing in the vicin-
ity.326 This could give the wild relatives immunity to their
natural enemies that normally keep them in check. With the
check gone, the plant could become a major weed. There
are areas of the world that serve as refugia for wild relatives
of major crops. These are the varieties to which breeders go
to obtain material for crop improvement. It would be un-
fortunate if this gene pool was altered by hybridization
with transgenic relatives. The transfer of marker genes
from cultivated to wild crops has already been shown to oc-
cur in oilseed rape, strawberries, and sunflowers. Trans-
Agrochemicals
genic Arabidopsis thaliana showed enhanced outcrossing
with wild relatives.327 Monarch butterfly larvae feeding on
milkweed plants covered with pollen from maize contain-
ing the B. thuringiensis gene died or were small or lethar-
gic.328 (Half of the monarch butterflies that overwinter in
Mexico come from the maize belt of the United States.)
There are some alternatives for reducing the damage to
maize by insects. The fungus Beauveria bassiana can live
in the maize plant and not hurt it, while at the same time be-
ing lethal to maize borers.329 Maize rootworms (which ma-
ture to beetles) are attracted to baits containing a curcur-
bitacin E glycoside.330 The baits can contain a red dye that
kills the worms when photoactivated by sunlight.
Many of the new transgenic crops (36%) are crops engi-
neered to be resistant to old herbicides.331 These include
bromoxynil (11.65) (LD50 111 mg/kg oral, mice) for cot-
ton, and glyphosate for maize, cotton, and soybeans.332
According to Monsanto, use of its transgenic soybeans
with glyphosate reduced herbicide use up to 10–35% with
no carryover in the soil that would limit crop rotation.
However, an analysis of 1998 crop data found “that soy-
beans engineered to resist the herbicide Roundup produced
yields 5 to 10% smaller than conventional seeds and re-
quired two to five times as much weed killer as conven-
tional soybeans.”333 Glyphosate is a relatively harmless
herbicide. There are still the problems of development of
resistance in weeds,334 transfer of genes to wild relatives
that might produce “superweeds,” soil erosion from soil
with no roots in it (when the crop is young), and spray drift
to sensitive plants nearby. Critics feel that this approach
merely reinforces the farmer’s reliance on pesticides. They
would rather see integrated weed management involving
crop rotation, choosing crops that outcompete weeds, in-
tercropping, planting at higher densities, and other me-
chanical and cultural practices described earlier in this
chapter.335
Another concern is that the antibiotic-resistance marker
genes used in current transgenic plants may make the an-
tibiotics involved useless in treating human diseases.336 It
is possible to produce transgenic crops without antibiotic
marker genes. Because transgenic crops contain foreign
11.65
347
proteins, it may be necessary to label the foods so that peo-
ple who may be allergic to these proteins can avoid them.
The host-specific nature of many insect viruses (bac-
uloviruses) was described earlier. Companies are studying
recombinant ones in an effort to provide faster killing of in-
sects or cessation of feeding, efficiency of action, longevity
in the field, and to extend the range of hosts.337 Because
one of their greatest advantages of baculoviruses is their
host specificity, it is probably a mistake to try to convert
them to agents with a wider spectrum of activity. Critics
also point out potential problems of the action of the altered
virus on beneficial insects or replacement of the old natu-
rally occurring virus.338 One altered baculovirus contains a
toxin from an Israeli scorpion that kills the insect in half the
usual time, even in a matter of hours.
VI. INTEGRATED PEST MANAGEMENT
Integrated pest management339 requires an understanding
of the ecology of the crop, the pest, and other plants and an-
imals in the system. It relies heavily on monitoring the pest
population. Ecologists and entomologists may be used as
consultants. When the level of the pest passes an economic
threshold340 that cannot be controlled by mechanical and
cultural means, additional special steps must be taken.
These may include augmenting the supply of predatory in-
sects, nematodes, fungi, or other organisms. Spraying is a
last resort. Then, the least harmful and most species-spe-
cific material is used in spot spraying of areas where the
pest population is high. Bacillus thuringiensis is often used
in place of chemical insecticides.
There have been some notable successes. In 1986, the
brown leafhopper had become a major pest of rice in In-
donesia. Before the use of insecticides began, it had been a
secondary pest. The government banned 57 out of 66 insec-
ticides for rice and removed subsidies from the rest. It gave
10 to 12-week–training courses in integrated pest manage-
ment to 200,000 farmers. As a result, pesticide applications
have been cut to 18% of their earlier amount, rice yields
have gone up 15%, and the government has saved 1 billion
dollars.341 The use of pesticides on rice in California’s Cen-
tral Valley has been reduced by 99% since 1985.342 It is pos-
sible to grow cotton without pesticides and without a trans-
genic variety. Tiny parasitic wasps and lacewing predators
are used along with pheromone traps.343 Organically grown
cotton sells for at least 40% more than regular cotton. The
amount of pesticides used on cotton in Texas has been re-
duced 90% since 1966.344 In Massachusetts, integrated pest
management has reduced pesticide use on apples, strawber-
ries, cranberries, maize, and potatoes by as much as
40–60%.345 It has been estimated that alternative agriculture
348
in Missouri could reduce soil loss 70%, energy use 22%,
herbicide use up to 40%, nitrogen fertilizer use up to 30%,
and production costs 17%.346 The U. S. National Arboretum
in Washington, DC, has used monitoring and spot spraying
to reduce its pesticide volume by three-fourths since
1992.347 It has also shifted to more horticultural oils, insec-
ticidal soaps, and insect growth regulators as alternatives to
chemical pesticides. Growers of apples and pears in the Pa-
cific Northwest are relying more and more on pheromone
mating disruption, sterile male and parasite releases, plus
spot spraying to control the codling moth.348 Areawide inte-
grated pest management in the United States in 1997 in-
cluded 7700 acres of apples and pears in the Pacific North-
west, 40,000 acres for the maize rootworm in the Corn Belt,
46,000 acres for leafy spurge, and 200,000 acres for the cot-
ton bollworm and tobacco budworm in Mississippi.349
An interesting experiment in low-input agriculture is
going on in Cuba today.350 Since Russian aid ended in
1991, the inputs of fertilizer, pesticides and petroleum have
dropped by more than 50%. Its pest-monitoring system is
said to be among the most comprehensive in the world.
There are many stations where mass rearing of beneficial
insects is done. Home gardens have proliferated. It is still
too early to tell how well this will work out.
Low-input, sustainable agriculture sometimes results in
reduced yields per acre, with 7–15% declines being com-
mon.351 This is offset, at least partially, by reduced costs
for fertilizers and pesticides. Low-input systems reduce
risk and variability in profits. A 15-year study in Pennsyl-
vania of farming without synthetic fertilizers and pesticides
using (a) legumes, grass, and cattle; and (b) maize and soy-
beans with all crop residues and manure returned to the
soil, found that yields and profits from maize were compa-
rable with those of a conventional system.352 There was
greater soil retention of carbon and nitrogen, together with
a 50% reduction of energy use.
Organic farming353 often caters to customers who will
pay more for a product. It has grown more than 20% a year
for the last 6 years.354 Significantly, 63% of organic farm-
ers are conducting their own on-farm research. In one area
of California, the top yield of rice is 100 bags of 100 lb. each
per acre. The organic farmer only obtained 85 bags, but sold
his rice for twice as much.355 In the Pacific Northwest, inte-
grated pest management has led to higher profits and lower
economic risk.356 In India, there was no difference in in-
come between conventional and sustainable agriculture.357
The current system of farm subsidies in the United
States is often mentioned as a barrier to low-input agricul-
ture.358 To remain in a price-support system, a farmer may
have to continue a monoculture with heavy inputs of fertil-
izers and pesticides and without crop rotation. Farm subsi-
dies in the United States are $8.5 billion/yr.359 Conven-
Chapter 11
tional economics assigns no cost to soil erosion, water pol-
lution, loss of biodiversity, loss of natural pollinators, and
global warming.360 If these costs were included, sustain-
able agriculture would come out ahead of conventional
agriculture.
In some cases, misconceptions led to the unnecessary
use of pesticides. Cotton farmers in the Imperial Valley of
California saw Lygus hesperus on the cotton and sprayed,
even though work at the nearby experimental station
showed the insects did not lower the yield of cotton.361 By
ignoring this and other recommendations based on local re-
search, the industry almost collapsed before it was revived
by the adoption of integrated pest management. Viet-
namese rice farmers sprayed leaf-folders until they were
shown by demonstration plots that the insects made no dif-
ference on the yield.362
Consumer expectations may be unrealistically high. Of
the pesticides used on oranges, 60–80% are just to improve
the cosmetic appearance of the skin.363 Homeowners may
grab the spray can instead of picking an insect off of a plant
or just pulling up a weed by hand. People who are fearful
of pesticide residues in their food may still use pesticides
freely in their yards and in their homes.
Large companies have been slow to enter the niche mar-
kets required by integrated pest management. They prefer
broad-spectrum products with large volumes, that are
patentable and provide some effective advantage over the
competition. The products must have acceptable toxicologi-
cal and environmental effects.364 They feel that the costs of
developing and registering a biopesticide that is highly spe-
cific cannot be recouped in the marketplace. Thus, govern-
ment agricultural experimental stations may have to develop
a product and then hunt for a small company to produce and
distribute it, or handle the whole operation themselves. Pro-
gressive chemical companies might look at the business
more broadly and develop an agricultural service for farm-
ers that involved monitoring services, beneficial insects
when needed, pheromones, or other services together with
ecologists and entomologists to help the farmer. Several
large companies are already in the business of supplying a
wide variety of small-volume products to customers (e.g.,
dyes and pigments, flavors and fragrances, stabilizers for
plastics, and soon). Studies have shown that small compa-
nies tend to be more innovative than larger ones.
REFERENCES
1. (a) G.W.A. Milne, ed., CRC Handbook of Pesticides, CRC
Press, Boca Raton, FL, 1995. (b) L.G. Copping and
H.G. Hewitt, Chemistry and Mode of Action of Crop
Protection Agents. R. Soc. Chem., Cambridge, 1998.
Agrochemicals
2. P.C. Kearney, D.R. Shelton, and W.C. Koskinen,
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Chapter 11
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RECOMMENDED READING
1. B. Hileman, Chem. Eng. News, Mar. 18, 1996, 23 [immune
system suppression caused by pesticides].
2. T. Eisner and J. Meinwald, eds., Chemical Ecology: The
Chemistry of Biotic Interaction, National Academy Press,
Washington, DC, 1995, 103–111 [chemistry of sex attraction
in insects].
3. G. Gardner, In: L. Starke, ed., State of the World 1996, WW
Norton, New York, 1996, 78–94 [preserving agricultural re-
sources].
4. [Alternate for Ref. 3] M. Mellon, J. Rissler, and F. McCa-
mant, Union of Concerned Scientists briefing paper, “Sus-
tainable Agriculture,” 1995.
5. I. Perfecto, Am. J. Alt. Agric., 1994, 9(3), 98 [integrated pest
management in Cuba].
6. R. Wrubel, Technol. Rev., 1994, 97(4), 57 [herbicide-resis-
tant crops].
7. P.A. Matson, W.J. Parton, A.G. Power and M.J. Swift, Sci-
ence, 1997, 277, 504 [problems with agrochemicals].
8. B. Hileman, Chem. Eng. News, July 19, 1999, 42 [transgenic
crops].
9. AS Moffat, Science, 1998, 279, 988 [global nitrogen over-
load].
EXERCISES
1. Visit a garden supply store to see what chemicals
are being sold for use around the home. Look up the
chemicals in the Merck Index and other suitable
sources to see what they are and what their toxici-
ties are. Include Scott’s four-step lawn care pro-
gram in the survey. If possible compare the levels of
application to those recommended by your local
agricultural extension agent for use on farm crops.
2. See if any of your neighbors use electric insect traps
and “Bag-A-Bug” traps. Neither is effective.
3. Compare prices of organic farm produce and con-
ventional produce in a local store.
4. See how many compost piles there are in your
neighborhood.
5. Check with your university agricultural department
to see what research is being conducted on sustain-
able agriculture.
6. Is there any contamination of ground or surface wa-
ter from agricultural or lawn runoff near where you
live? If so, what are the sources? Propose some so-
lutions for any problems that may have resulted
from it.
12
Materials for a Sustainable Economy
I. INTRODUCTION
Most organic chemicals in use today are derived from non-
renewable petroleum and natural gas, with some still being
made from coal. After use, the bulk of these ultimately end
up as carbon dioxide, the main greenhouse gas that is caus-
ing global warming. For a sustainable future1 these must be
based on renewable resources2 from fields and forests. Be-
fore the advent of cheap petroleum and natural gas, many
of them were. It is instructive to look back at these older
methods to see if they might be economical today if the cost
of global warming were included in the prices of the or-
ganic chemicals that we use. Further optimization of the
processes with the knowledge that has accumulated since
they were in use should increase yields and lower costs.
Biocatalysis (see Chap. 9) is an example. Formerly it was
used more for the production of commodity chemicals than
it is today. Some of these earlier fermentation methods
have not been studied much lately. Because energy is often
a large factor in producing chemicals, renewable sources
(see Chap. 15) will have to replace the fossil fuels used to-
day. The adoption of such sources of energy and raw mate-
rials will cut the amount of acid rain substantially, for there
is not much sulfur in either the raw materials or the fuels.
The following sections will explore routes to the basic
chemicals that are now in use, as well as some new possi-
bilities. They should be read in conjunction with one of the
standard texts3 on industrial organic chemistry. (Specific
references will not be given for well-known processes in
these texts.) Carcinogens and very toxic chemicals will be
avoided where possible. Energy-intensive processes will
be avoided, if there is more than one possible route. Some
methods of converting oil and natural gas to commodity
chemicals use as much as one-third of the starting material
for energy to fuel the process. They often involve high tem-
359
peratures, with low conversions, and much recycling.
Sometimes, it is necessary to quench a hot stream to obtain
the desired product. After the product is separated, the
stream must be reheated to the high temperature for the
next cycle. Many of today’s processes involve oxidation of
the starting hydrocarbon to move oxygen into the
molecule. Renewable raw materials have oxygen in them,
so that converting them to the desired products involves
different methods, which may not require such extreme
temperatures and so much energy. Although biogas
(methane) derived from anaerobic fermentation of organic
matter could be used with today’s processes for natural gas,
there would not be enough of it.
II. COMMODITY CHEMICALS FROM
RENEWABLE RAW MATERIALS
The 50 largest-volume chemicals contain many derived
from fossil carbon sources. Their 1995 volumes in billions
of pounds produced in the United States4 are ethylene
(46.97), ammonia (35.60), propylene (25.69), methyl tert-
butyl ether (17.62), ethylene dichloride (17.26), nitric acid
(17.24), ammonium nitrate (15.99), benzene (15.97), urea
(15.59), vinyl chloride (14.98), ethylbenzene (13.66),
styrene (11.39), methanol (11.29), carbon dioxide (10.89),
xylene (9.37), formaldehyde (8.11), terephthalic acid
(7.95), ethylene oxide (7.62), toluene (6.73), p-xylene
(6.34), cumene (5.63), ethylene glycol (5.23), acetic acid
(4.68), phenol (4.16), propylene oxide (4.00), butadiene
(3.68), carbon black (3.32), isobutylene (3.23), acryloni-
trile (3.21), vinyl acetate (2.89), acetone (2.76), butyralde-
hyde (2.68), cyclohexane (2.13), adipic acid (1.80), ni-
trobenzene (1.65), and bisphenol A (1.62). Ammonia is
included because the hydrogen used in its synthesis is de-
360
rived from methane or another fossil hydrocarbon. Many of
these compounds are intermediates in the synthesis of poly-
mers. Polyethylene is the world’s most common plastic
(41% of the total), with others including polyvinyl chloride
(23%), polypropylene (21%), polystyrene (11%) and acry-
lonitrile–butadiene–styrene plus styrene–acrylonitrile
copolymers (4%).5
A. Olefins and Chemicals Derived from Them
Ethylene for polymerization to the most widely used
polymer can be made by the dehydration of ethanol from
fermentation (12.1).6 The ethanol used need not be anhy-
drous. Dehydration of 20% aqueous ethanol over HZSM-5
zeolite gave 76–83% ethylene, 2% ethane, 6.6% propy-
lene, 2% propane, 4% butenes, and 3% n-butane.7 Pre-
sumably, the paraffins could be dehydrogenated catalyti-
cally after separation from the olefins.8 Ethylene can be
dimerized to 1-butene with a nickel catalyst.9 It can be
trimerized to 1-hexene with a chromium catalyst with
95% selectivity at 70% conversion.10 Ethylene is often
copolymerized with 1-hexene to produce linear low-den-
sity polyethylene. Brookhart and co-workers have devel-
oped iron, cobalt, nickel, and palladium dimine catalysts
that produce similar branched polyethylene from ethylene
alone.11 Mixed higher olefins can be made by reaction of
ethylene with triethylaluminum or by the Shell higher
olefins process, which employs a nickel phosphine
catalyst.
The catalytic dehydrogenation of 1-butene gives 1,3-
butadiene,12 which can be dimerized to 4-vinyl-1-cyclo-
hexene by a copper(I)-containing zeolite, with over 99%
selectivity.13 This material is converted to styrene by
catalytic oxidation with oxygen in the presence of steam
12.1
Chapter 12
with 92% selectivity. This can provide the styrene for
conversion to polystyrene and to styrene–butadiene
rubber. Isobutene, for reaction with methanol to produce
methyl tert-butyl ether, an antiknock agent for gasoline,
and to make polyisobutylene rubber, used as the liner
of tires, can be made from 1-butene by acid-catalyzed
isomerization.
Propylene can be produced by the metathesis of ethy-
lene and 2-butene, obtained by the catalytic isomerization
of 1-butene.14 Tungsten- or molybdenum-containing cata-
lysts are used. Because the reaction is reversible, an excess
of ethylene will help drive the reaction to propylene. A
mixture of acetone and 1-butanol can be made by the fer-
mentation of sugars. Propylene could be produced by cat-
alytic hydrogenation, followed by dehydration of the inter-
mediary isopropyl alcohol. The 1-butanol could be
dehydrated to 1-butene, which could be isomerized to 2-
butene for metathesis with ethylene to produce more
propylene. Thus, two fermentation plants could convert
sugars from the hydrolysis of carbohydrates to ethylene
and propylene. These two monomers are used to make
large volumes of plastics, especially because they are inex-
pensive. They may not enjoy such an economic advantage
over other plastics if they are made by the fermentation
routes. Copolymers of ethylene and propylene are used
as rubbers. Elastomeric polypropylene can be prepared
from propylene alone using metallocene catalysts.15 Ethy-
lene–propylene copolymers with the properties of plasti-
cized polyvinyl chloride can also be prepared with metal-
locene catalysts.16
Thermoplastic engineering resins are being made by the
copolymerization of ethylene with carbon monoxide (12.2)
with a small amount of propylene present in the mixture.17
The process also works with higher olefins.
Materials for a Sustainable Economy
12.2
A third possible route to propylene converts sugars to
propionic acid by fermentation. (Propionic acid has also
been made by the hydroxycarbonylation of ethylene using
a molybdenum-containing catalyst.18) The propionic acid
would be hydrogenated catalytically as such, or as an ester,
to 1-propanol (12.3), which could be dehydrated to
propylene.
Numerous other large-volume compounds can be made
from ethylene and propylene by standard petrochemical
methods. Ethylene can be oxidized to ethylene oxide using
oxygen with a silver catalyst (12.4). Propylene can be oxi-
dized to propylene oxide with hydrogen peroxide and tita-
nium silicalite (see Chap. 4). Vinyl chloride (a carcinogen)
is produced by adding chlorine to ethylene, followed by
12.3
12.4
361
cracking the resultant ethylene dichloride. Vinyl acetate is
made by the oxidative addition of acetic acid to ethylene
using a palladium catalyst. A corresponding addition of
water to ethylene gives acetaldehyde, which might be made
more directly by the oxidation of ethanol from fermenta-
tion. It was formerly made by copper-catalyzed dehydro-
genation of ethanol or by silver-catalyzed oxidation of
ethanol with air.
Acrylic acid for acrylic ester monomers is made by the
air oxidation of propylene to acrolein, then to acrylic acid
(12.5).19 Methacrylic acid for methacrylates can be made in
the same way from isobutylene.20
Citric acid derived from sugars by fermentation can be
converted to methacrylic acid with hot water (as mentioned
in Chap. 8). Acrylonitrile (a carcinogenic monomer) is
made by the oxidation of propylene with a mixture of am-
monia and oxygen.21
Eastman Chemical has devised a way to convert 1,3-bu-
tadiene to various commodity chemicals by way of 3,4-
epoxy-1-butene (12.6).22
Another route to tetrahydrofuran starts with furfural
obtained by the acidic dehydration of pentose sugars
362
12.5
12.6
found in oat hulls, maize cobs, and other vegetable
wastes. Catalytic decarbonylation gives furan, which is
reduced to tetrahydrofuran. Tetrahydrofuran can be poly-
merized to glycols used in making polyurethanes by reac-
tion with diisocyanates. The 1,4-butanediol is used in
making poly(butylene terephthalate). Dehydrogenative
cyclization of 1,4-butanediol yields butyrolactone, which
can be converted to pyrrolidones by treatment with am-
monia or amines (12.7). The monomer, N-vinyl-2-pyrroli-
done, is made by vinylation of 2-pyrrolidone with acety-
lene. It might be possible to do the vinylation with
acetaldehyde instead.
12.7
Chapter 12
B. Alcohols and Carboxylic Acids
The preparation of 1,3-propanediol from glucose or glyc-
erol by biocatalysis was described in Chap. 9. It is used in
making poly(trimethylene terephthalate). Ethylene glycol
and 1,2-propanediol are obtained by the hydrolysis of the
corresponding epoxides. A mixture of ethylene, propylene,
and butylene glycols, together with a small amount of glyc-
erol, has been produced in 94% conversion by the hy-
drogenolysis of sorbitol with a Ru/Sn on carbon catalyst in
the presence of sodium hydroxide.23 Sorbitol is obtained by
the reduction of glucose (see also work by Wang et al.24).
Materials for a Sustainable Economy
12.8
Ethyl acetate can be obtained by the dehydrogenation of
ethanol in 95.7% yield.25 The process may involve a dis-
proportionation of the intermediate acetaldehyde. It can
also be made by direct esterification of ethanol using acetic
acid made by fermentation. Acetone was prepared in
97–98% yield by treatment of acetic acid with cerium(IV)
oxide on silica26 or manganese nodules from the Indian
Ocean.27 This is an alternative to the fermentation that pro-
duces it along with 1-butanol and might be preferable, in
that any process that produces two coproducts must find
adequate outlets in the market for both of them. There is a
loss of one carbon when acetic acid is converted to acetone.
Succinic acid has been produced in 90% yield by the
anaerobic fermentation of carbohydrates.28 It was heated to
form succinic anhydride, which was then oxidized to
maleic anhydride with oxygen, using an iron phosphate
catalyst (12.8) in more than 95% selectivity at up to 58%
conversion.
Maleic anhydride can also be made by the air oxidation
of butenes. Maleic anhydride is used in the preparation of
unsaturated polyester resins. It can also be reduced to buty-
rolactone and to 1,4-butanediol. It also offers a possible
synthesis of phthalic anhydride by a Diels–Alder reaction
with 1,3-butadiene (12.9).
Phthalic anhydride is used in the preparation of alkyd
and other resins, as well as in the preparation of esters (e.g.,
di-2-ethylhexyl phthalate) which serve as plasticizers for
polyvinyl chloride. It can also be converted to terephthalic
acid for the preparation of poly(ethylene terephthalate)
12.9
363
through potassium phthalate using the Henkel process
which employs a zinc–cadmium catalyst at high
temperatures.
Lactic acid can be produced by fermentation of starch
wastes or cheese whey.29 It has also been prepared from
ethylene, carbon dioxide, and water using a Pt /Sn /SiO2
catalyst.30 It can be converted to an analogue of maleic an-
hydride by a two-step oxidation (12.10).31
This anhydride may be suitable for some of the uses of
maleic anhydride in the preparation of polymers. Dehydra-
tion of lactic acid to the important monomer, acrylic acid,
gave only a 17% yield.32 Pyrolysis of the acetate of methyl
lactate gave methyl acrylate in 90% yield, but was reported
to be too expensive to use commercially. Oligomers of lac-
tic acid can be prepared by simple heating.33 It may be pos-
sible to pyrolyze them to acrylic acid in high yields.
Adipic acid for the preparation of nylon is made starting
with benzene. It can be made from glucose via catechol, as
shown by Frost and co-workers (see Chap. 9). It can also be
made by the oxidation of petroselenic acid with ozone
(12.1), the companion product lauric acid also being
valuable.34
O3
CH3(CH2)10CHBCH(CH2)4COOH →
(12.1)
CH3(CH2)10COOH  HOOC(CH2)4COOH
Petroselenic acid constitutes 70–80% of the seed oil of
many species of Umbelliferae. This requires growing a
new crop or putting the appropriate genes into a microor-
ganism or higher plant (such as rapeseed). It may be possi-
364
12.10
ble to prepare adipic acid from glucose by a chemical route.
Glucose can be oxidized to an – dicarboxylic acid (glu-
caric acid) by air with a platinum catalyst.35 The next step
would be to replace all of the hydroxyl groups with hydro-
gen. This has been done with tartaric acid using hydrogen
iodide (12.11).36 The challenge is to make it catalytic in io-
dide or to find another system of reduction.
Another way to prepare dibasic acids for the preparation
of polyamides would be to oxidize cyclohexene from the
Diels–Alder reaction of 1,3-butadiene and ethylene or cy-
clooctene made from 1,3-butadiene by cyclic dimerization,
followed by a reduction that might involve conjugation of
the double bonds in situ (12.12). The latter may be prefer-
able because the former requires forcing conditions.37 It
may be possible to run the former reaction under high pres-
sure or with ultrasound or with a metal complex catalyst
(such as a metal triflate) to reduce the electron density of
the diene by complexation.
The diamines needed for the polyamides can be made by
conversion of the acids to their ammonium salts followed
by heating to form the dinitriles, which can then be re-
duced. Adipic acid can be reduced to 1,6-hexanediol (for
use in polyurethanes) with hydrogen in 95% yield using a
modified platinum catalyst.38 Earlier processes, which
12.11
Chapter 12
went through the dimethyl ester, gave a 90% yield. Adipic
acid can be reduced with hydrogen in the presence of ex-
cess pivalic anhydride with a palladium catalyst to produce
adipaldehyde in 94–99% yield.39 The pivalic acid formed
in the reaction is reconverted to pivalic anhydride for the
next run. The by-product pivaldehyde can be oxidized to
pivalic acid for reuse. Adipaldehyde might be used to
cross-link proteins (e.g., in the immobilization of enzymes
or in the tanning of leather. Dialkyl adipates can also be
made by the tail to tail dimerization of alkyl acrylates using
palladium or other metal catalysts (12.13).40
Paper mill sludge (as well as other forms of cellulose)
can be converted to levulinic acid in 70–90% yield by hy-
drolysis to glucose followed by controlled heating (12.14)
in a process developed by Biofine, Inc.41
Levulinic acid can be converted by known processes to
the solvents, tetrahydrofuran and 2-methylfuran, to suc-
cinic acid, to 5-aminolevulinic acid for weed control (see
Chap. 11) and to diphenolic acid. Diphenolic acid may be
useful in waterborne epoxy coatings and other resins. If a
suitable acid catalyst that can be left in the resin can be
found, it may be possible to convert diphenolic acid, by
self-acylation, to an analogue of phenol–formaldehyde
resins, thus eliminating the use of the carcinogenic
Materials for a Sustainable Economy 365

12.12

12.13

12.14
366
formaldehyde. The by-product formic acid and furfural
may also be valuable.
C. Epoxides and Aromatic Compounds
Many epoxy resins are based on the diglycidyl ether of
bisphenol A, made by the reaction of epichlorohydrin (very
toxic) with the diol in the presence of base (12.15).
A better system that avoids the toxic reagent and the by-
product salts would be to use epoxides derived from 4-
vinyl-1-cyclohexene, 1,5-cyclooctadiene, oligomeric
poly(butadiene), unsaturated oils, terpenes, and such, that
come from renewable sources or can be derived from them
as outlined in the foregoing. This will require considerable
redesign of the resins. Epoxidized vegetable oils mixed
with diepoxides, glass fiber, and a photocationic initiator
have been polymerized with sunlight to give materials suit-
able for roofing, culverts, boats, medical casts, and pipe.42
The starting resins are nontoxic, have an infinite shelf life
in the dark, and need no refrigeration. Bisphenol A is also
used in the preparation of polycarbonate resins. Its prepa-
ration requires a renewable source of phenol. Styrene can
be reduced to ethylbenzene which can then be oxidized to
the hydroperoxide, followed by cleavage to phenol and ac-
12.15
Chapter 12
etaldehyde with an acid catalyst (12.16). The styrene might
be oxidized to benzoic acid, for which conversion to phe-
nol is known.43 Benzoic acid can also be converted to
terephthalic acid by the Henkel process.
The benzoic acid might also be made by the Diels–Alder
reaction of 1,3-butadiene with acrylic acid followed by cat-
alytic dehydrogenation. Treatment of phenol with ammo-
nia at high temperatures produces aniline, as mentioned in
Chap. 2. Ethylbenzene can be rearranged to xylenes with
zeolite catalysts. Thus, it could serve as a source of ph-
thalic, isophthalic, and terephthalic acids by the oxidation
of o-, m-, and p-xylenes. (The xylenes and other aromatic
hydrocarbons can also be made by the dehydrocyclization
of ethylene, propylene, and butenes, or their corresponding
alkanes.44 Benzene can also be made from methane.195)
p-Cresol can be made from p-cymene derived from ter-
penes by dehydrogenation (12.17).
It might then be oxidized enzymatically with hydrogen
peroxide to produce a polymer, as described in Chap. 9. A
final cure with diisocyanates or bisoxazolines would yield
the equivalent of a phenol–formaldehyde resin without use
of the carcinogenic formaldehyde. Terephthalic acid for
poly(ethylene terephthalate) might be made by the oxida-
tion of p-cymene, although two carbon atoms would be
Materials for a Sustainable Economy 367

12.16

lost. The amount of terpenes available may not be enough

for this use.
Catechol, hydroquinone, and pyrogallol can be pro-
duced from glucose by the enzymatic methods of Frost and
co-workers (see Chap. 9). Catechol can also be obtained by
the demethylation and cleavage of lignin, the polymer that
holds wood together.45 Frost and co-workers have shown
how to convert catechol to adipic acid. Thus, the lignin
from wood, which is now underutilized, might be con-
verted into nylon.
A major use of phenol is in phenol–formaldehyde adhe-
sives for wood. Tannins are polyphenols from plants, as in
bark,46 that may be able to replace phenol in such adhe-
sives. A typical repeating unit is shown in (12.18).
These repeating units are often linked by C4–C6 or
C4–C8 bonds. Some tannins can be hydrolyzed to gallic
acid (12.19). The atoms in the ring are numbered. Typical
dehydrodimers are connected through the number 4 carbon 12.18
atom of one ring to number 8 of the other and in the second
case number 4 to number 6 of the other.
The pyrogallol was reacted with formaldehyde to give
resins comparable with those made from phenol.47 Per-

12.17
368
12.19
haps furfural can be used instead of formaldehyde. The
most interesting adhesives from tannins use no formalde-
hyde and have no toxicity. They are made by the self-con-
densation of tannins in the presence of silica and sodium
hydroxide, or other catalysts. The heterocyclic ring opens
to yield a reactive 2-position which substitutes open posi-
tions in the aromatic rings of the adjacent chains of tan-
nins.48 This is suitable for interior use. Further study or
the addition of organic cross-linking agents such as diiso-
cyanates might make it suitable for boards for exterior
use. The use of tannins is attractive because the waste tree
bark (from which they are often obtained) is frequently
located next to the plywood or particle board mill. Sys-
tems such as this may also be useful in tanning leather
without the use of chromium. Lignins, which are also
polyphenols, can also be used as adhesives for wood with-
out formaldehyde. The soluble lignin can be cross-linked
oxidatively with a hydrogen peroxide plus sulfur dioxide
redox system or with diepoxides, diisocyanates, and
such.49 It should be possible to use a nonvolatile reducing
agent instead of sulfur dioxide.
D. Chemicals from Fats and Oils196
Fats and oils (triglycerides) from plants and animals are re-
newable sources of chemicals, but the amounts of the
chemicals made from them are small compared with those
made from petroleum and natural gas. This may change if
biodiesel fuel (e.g., ethyl oleate) made by the alcoholysis of
oils becomes common. Such esters may be useful as envi-
ronmentally friendly solvents.50 Unsaturated oils, such as
linseed oil, are the basis of oil-based paints, which cure by
cross-linking through oxidation by air. Soaps are the potas-
sium or sodium salts of the long-chain fatty acids obtained
by the hydrolysis of the triglycerides. The dibasic dimer
fatty acids obtained by the dimerization of oleic and
linoleic acids (both C18 acids) are made into oligomeric
fatty amides which are used to cure epoxy resins. The un-
Chapter 12
saturated oils are also epoxidized to epoxides for use in
epoxy resins and as stabilizers for plastics. There are also
efforts to raise Vernonia galamensis that naturally contains
epoxy oils.51
Hydrogenation of fats and oils leads to long-chain alco-
hols that can be converted to sulfate detergents, such as
sodium lauryl sulfate. These alcohols can also be converted
to acetals of sugars, the alkyl glycoside detergents.52 (See
Chap. 3, Sec. VII and Chap. 8, Sec. VI for more on “green”
detergents.) Fatty amines are obtained by reduction of fatty
nitriles, which are made by heating the ammonium salts of
the fatty acids. These can be made into quaternary ammo-
nium salts for use as detergents, phase transfer catalysts
and germicides.
Castor oil contains 90% ricinoleic acid residues, so that
it has a hydroxyl functionality of about 2.7.
CH3(CH2)5CH(OH)CH2CHBCH(CH2)7COOH
ricinoleic acid (12.2)
The reaction of castor oil with diisocyanates has been used
to make polyurethanes.53 In one case, hydroxyethyl-
methacrylate was included to form a prepolymer with a ter-
minal methacrylate group that could be cured with benzoyl
peroxide. Heating a mixture of ricinoleic, maleic, and se-
bacic acids in a melt produced a polyanhydride with a
molecular weight of over 100,000, which could be used as
a biodegradable polymer for slow drug release.54
Vegetable oils can also be used as food-grade lubricants
after the addition of antioxidants.55 A genetically engi-
neered soybean oil from duPont contains 80% monounsat-
urated acid residues and 6% polyunsaturated ones.56 It can
be used as a hydraulic fluid or as a food-grade lubricant.
Biodegradable ester hydraulic fluids with triple the stabil-
ity of mineral oil-based ones can be made by treating un-
saturated fatty acids from vegetable oils with sulfuric acid
(to cause addition of the carboxylic acid group to the dou-
ble bond).57 The use of various fatty acid esters as cutting
oils for metal working is covered in Chap. 13.
Materials for a Sustainable Economy
12.20
Both fatty and resin acids (diterpene acids) are obtained
as a by-product of the pulping of wood for paper. The mix-
ture is known as tall oil. The separated resin acids are
known as rosin. Resin acids such as abietic acid (12.20) can
also be obtained as exudates of pine trees.
Paper is often sized by forming the aluminum salt of
rosin on it. This allows printing on paper by keeping the ink
from soaking into it. Esters of rosin with alcohols such as
glycerol and pentaerythritol are used as tackifying resins
for adhesives. These “hard resins” compete with
oligomeric resins made from petroleum fractions.58
E. The Use of Synthesis Gas from Biomass
Synthesis gas is usually made from natural gas or
petroleum. It can also be made from biomass59 and from
municipal solid waste.60 This mixture of carbon monoxide
and hydrogen can then be converted to a variety of materi-
als by standard petrochemical methods (12.21), using a va-
riety of catalysts.61
The water–gas shift reaction is used to convert the car-
bon monoxide to carbon dioxide and more hydrogen.
These, when reacted under the influence of the special cat-
12.21
369
alyst, form ethanol with 83% selectivity.62 The hydrogen
can be used to reduce the carbon monoxide to methanol.
The synthesis gas can also be used in the hydroformylation
of olefins to form aldehydes.63 It can be converted to gaso-
line via the Fischer–Tropsch reaction.64 If the iron catalyst
is supported on MgO/SiO2, the yield of C2–C4 olefins is in-
creased to a ratio of 0.65 olefins to paraffins.65 The Mobil
process converts methanol to gasoline over a zeolite. If the
process is run at 538°C, a higher temperature than usual,
the product consists of 60.5% C1–C4 aliphatics, 3.5%
higher aliphatics, 35.9% xylenes, and 0.1% aromatics of
more than C11.66 This is one way to produce the xylene
needed to make terephthalate polymers. When canola oil
was used instead of the methanol in this process, a maxi-
mum yield of C2–C4 olefins of 26% was obtained.67 Aro-
matic compounds were also produced at the same time. An
aluminum phosphate catalyst converted methanol (77%
conversion) to a mixture in which more than two-thirds of
the products were ethylene and propylene.68 The selectiv-
ity for ethylene was 58% and that for propylene was 21%.
Ammonia is produced by the reaction of nitrogen with
hydrogen derived from petroleum or natural gas. This pro-
cess uses 60% of all the hydrogen produced. Hydrogen
from the electrolysis of water costs quite a bit more. The
hydrogen could be made from biomass as shown in 12.21.
Ammonia can be reacted with carbon dioxide to form urea,
much of which ends up in slow-release fertilizer. The use
of leguminous cover crops to put nitrogen into the soil
could reduce the demand for fertilizers based on ammonia
or urea (as described in Chap. 11). Melamine for
melamine–formaldehyde resins is made by heating urea
with an aluminum oxide catalyst (12.22).
These resins are used in counter tops and plastic dinner-
ware. It should be possible to replace the carcinogenic
formaldehyde with various cross-linking agents, such as
glyoxal, bisanhydrides, bisepoxides, bisoxazolines, diiso-
cyanates, and the like.
370
12.22
III. USE OF NATURAL POLYMERS
Before advent of cheap petroleum, many natural polymers
were being used or being studied for use in plastics. Since
then, synthetic polymers have dominated the marketplace.
It should be possible to make the plastics that we need from
cellulose, hemicellulose, starch, chitin, lignin, proteins, or
other natural products.69 Ideally, the plastic or other prod-
uct should have properties similar to or better than the one
derived from petroleum that it is to replace. It should not re-
quire more energy to make or cost more.
A. Cellulose
Cellulose (12.23)70 is found in wood, along with about
24% hemicellulose and 22% lignin, and in cotton, sisal,
jute, linen, hemp, and other similar products. It is a polymer
of glucose.
It can also be made from sucrose by Acetobacter
xylinum.71 This bacterial cellulose has high mechanical
strength and might become an important material if the cost
can be brought down. Regenerated cellulose fibers are
known as rayon and regenerated films as cellophane. They
are usually made by the xanthate process, which uses
sodium hydroxide and carbon disulfide.
NaOH CS2
CellOH → CellONa  → (12.3)
H
CellOC(S)SNa 
 → CellOH
The xanthate solution is converted to fiber or film by
passage into a bath of acid. This relatively polluting pro-
cess is being replaced by one in which a solution of cellu-
12.23
Chapter 12
lose in N-methylmorpholine-N-oxide is passed into wa-
ter.72 The solvent is recovered and recycled. This method
produces stronger materials, because the resulting molecu-
lar weight is higher. The product costs twice as much as
cotton, a price that does not take into account the environ-
mental effects of the large amount of irrigation water, fer-
tilizer, and pesticides required by the crop. (The drying up
of the Aral Sea is one result.) If cellulose from trees can be
used in this process, these environmental problems would
be reduced. Trees also have the advantage that they can be
harvested any time of the year, in contrast with the seasonal
harvesting of an annual crop.73 Steam-exploded wheat
straw can be used as a source of cellulose for making
rayon.74
Kenaf also avoids some of these problems, but is an an-
nual crop. Its 50:50 blends with cotton perform as well in
textiles as 100% cotton, while having better luster, texture,
dye uptake, and colorfastness.75 Linen (from flax which
does not require as much water to grow as cotton) has han-
dle, comfort, strength, and water absorption properties su-
perior to cotton, but it has less than 1% of the market. Ef-
forts are being made to make it easier to use by improving
the processes by which the fibers are separated from the
rest of the plant. This retting is usually done by leaving the
plants in a wet place in the field for a few weeks. The new
methods involve heating with sodium dodecylsulfate and
oxalic acid in water for 2 h at 75°C76 or steam explosion.77
The tenacity of flax can be improved 50% and that of jute
110% by grafting on some methyl methacrylate or 2-hy-
droxyethyl methacrylate.78 The flax plant can serve as a
source of both fiber for clothing and of oil for paints, epox-
ides, and such.
A possible way to lower the cost of fibers and films of
regenerated cellulose would be to run cellulose through a
twin-screw ultrasonic extruder with a minimum of the sol-
vent and passing the exudate through a stream of hot air to
recover the solvent for reuse. This stronger cellophane
could be used in place of many plastic films used today.
The high moisture vapor transmission of cellophane is re-
duced by a coating of nitrocellulose or poly(vinylidene
chloride), which also makes the film heat-sealable.79 Cel-
Materials for a Sustainable Economy
lulose, in the forms of wood flour, bamboo fiber, and such,
has also been used as a filler or reinforcing agent for
plastics.80
A great many derivatives of cellulose, principally esters
and ethers, have been made. Methyl, ethyl, carboxymethyl,
hydroxyethyl, and hydroxypropyl ethers are made com-
mercially today. These are used as water-soluble polymers,
except for ethylcellulose which is a tough plastic used in
screw driver handles, and such. Methylcellulose plasticized
with polyethyleneglycol has been tested as an edible coat-
ing for preventing water loss from fruit.81 An alternate uses
microemulsions of beeswax, candelilla wax, or carnauba
wax to deposit the edible film on fruit.82 Cellulose acetate
and cellulose acetate butyrate are also commercial plastics.
The main factor inhibiting the larger use of these cellulose
derivatives is their higher cost relative to polyolefins and
other plastics derived from petroleum and natural gas. If
simpler, cheaper methods for the preparation of the cellu-
lose derivatives can be devised their competitive situation
should improve.
It may be possible to prepare many cellulose deriva-
tives in extruders, with or without the addition of ultra-
sound and microwaves. If acetic anhydride were used, the
by-product acetic acid could be removed through a vent.
If a cyclic anhydride, such as maleic or succinic anhy-
dride, were used, there would be no need for the vent. The
product should dissolve in aqueous base and might be
useful in situations in which sodium carboxymethylcellu-
lose is used today. Polymeric anhydrides might also be
used. (Cellulose acetate has been reacted with cyclic lac-
tones in an extruder.83) Methylcellulose might be made
with dimethyl carbonate in the presence of a base. It
should be possible to design reagents to disrupt the hy-
drogen bonds of cellulose, then react with it in the ex-
truder. Solvents for cellulose such as N-methylmorpho-
line-N-oxide, lithium chloride–N, N-dimethylacetamide84
and ammonia–N, N-dimethylformamide85 can serve as a
starting point for ideas. The simplest would be to make a
cellulose carbamate using urea. Grafting on N,N-dimethy-
lacrylamide, N-acryloylmorpholine, N-vinylpyrrolidone,
and such, with or without N, N-methylenebisacrylamide as
a cross-linking agent, may also be possible. The amide
could also be made in situ by reaction of the cellulose
with isocyanates or oxazolines. Formaldehyde is used
with some solvents to dissolve cellulose. Perhaps an alde-
hyde, such as butyraldehyde or furfural could be used in
the extruder along with other reagents that would react
with the cellulose, but not with the aldehyde. A final pos-
sibility would be to see if a little aldehyde plus water
could be extruded, with a vent for the water at the end. An
acid catalyst may be necessary to form the acetals in these
reactions.
371
Trimethylsilylcellulose has been prepared from cellu-
lose and 1,1,1,3,3,3-hexamethyldisilazane in liquid ammo-
nia in an autoclave.86 There were no by-product salts, no te-
dious purification, and no degradation of the polymer
chain. Such a process might be run in an extruder. The cost
of the reagent may be a drawback to widespread use.
B. Starch
Starch is also a polymer of glucose, but with -glucosidyl
linkages instead of the  ones in cellulose. It consists of a
linear polymer, amylose, and a branched polymer of much
higher molecular weight, amylopectin.87 Starch fibers ex-
truded from a mixture of high-amylose cornstarch contain-
ing 30% water have been suggested for use in paper and
textiles.88 Before they can be used, their resistance to water
needs to be increased by some sort of cross-linking, per-
haps with glyoxal or adipaldehyde. Compression-molded
high-amylose starch containing water and or glycerol is
tough.89 It is stronger when cellulose microfibrils are
added.90 Because plasticizers can evaporate, migrate, or
leach out over time, it might be wise to try some of higher
molecular weight, such as polyglycerol or polyethylene ox-
ide. Plates, eating utensils, and other items have been
molded from starch containing some water or glycerol.91 It
is best to add a coating to increase the resistance to water.
Perhaps, cutin, the outer covering of leaves, or waxes from
the outsides of fruits, can be recovered from food-process-
ing wastes and used for this purpose. A sucrose oleate
might act both as a plasticizer and a hydrophobic agent.
A composite of limestone, potato starch, and a small
amount of cellulose fiber is being tested for containers used
in fast-food restaurants.92 Foamed “peanuts” of starch for
packing purposes are available commercially for use in
place of those made of polystyrene.93
Tough leathery plastics have been made by extrusion of
a starch–methyl acrylate graft copolymer.94 It is possible
that the grafting could also be done in the extruder, de-
scribed earlier for cellulose. Because starch is more
tractable than cellulose, it should be possible to prepare
many derivatives in extruders. Use of some hydrophobic
reagents might remedy some of the problems of water re-
sistance. Another way to improve the resistance to water is
the use of polymer blends. Starch has been blended with a
copolymer of ethylene and vinyl alcohol for this purpose.95
Foamed plates have been prepared by baking a mixture of
starch and aqueous polyvinyl alcohol.96 Water or glycerol
was still required as a plasticizer in both. Plates, knives,
forks, and such, have been made by molding 30% of a syn-
thetic polyester with 70% starch or gluten.97 (The polyester
probably attachs to the starch or gluten by formation of an
ester or amide.) It is possible that a polymer made from re-
372
newable materials [e.g., poly(3-hydroxybutyrate) or poly-
lactate] would also work. Foamed polyurethanes have been
made from starch, polycaprolactone, water, and an
aliphatic diisocyanate.98
Rapidly dissolving water-soluble films have been made
from mixtures of pectin, starch, and glycerol.99 Water-sol-
uble films are useful in packaging materials that are to be
dissolved in water, such as food ingredients, detergents,
and pesticides. Dissolving the whole package eliminates
the problem of disposing of the package.
C. Hemicellulose and Chitin
The hemicellulose100 from the pulping of trees for paper is
an underused resource. A small amount is being hy-
drolyzed to xylose for hydrogenation to the sweetener, xyl-
itol.101 A good use would be as a substrate for fermenta-
tion. Apple waste consisting of 14% pectin, 12%
hemicellulose, and 41% lignocellulose can be injection
molded.102
Chitin103 is another underused resource. It is the second
most abundant polymer on earth, found in crab shells,
shrimp shells, and so on. It is a polymer of an acetylated
glucosamine (where the 2-OH is replaced by 2-
NHCOCH3). The amine from the hydrolysis of chitin is
called chitosan. Although many uses have been explored,
neither polymer has found widespread use. Chitin can be
converted to fibers by making a dibutyryl derivative.104
Such a derivatization might also be tried in an extruder.
Fibers have been spun from chitosan.105 Chitosan that has
been partially acylated to introduce acetyl, butyryl, hex-
anoyl, or lauroyl groups has been spun from aqueous solu-
tion.106 Subsequent heating to higher than 180°C gave
fibers with high-tensile strength and modulus that were in-
soluble in water and formic acids. The use of chitosan as a
coagulant for the wastewater from making tofu has been
described as using one waste to treat another.107 The prod-
uct is suitable for animal food.
D. Lignin
Most lignin108 from the pulping of wood for paper is burned
for fuel. Many efforts have been made to find higher-value
uses for it. Nearly all of it is removed from wood in a Kraft
process that puts sulfonate groups into it. (The structure
varies with the species. A schematic structure for spruce
lignin is shown on the following page (12.24).109 More phe-
nolic groups are formed in the pulping process.) A new pro-
cess, which may not yet be commercial, removes the lignin
from the wood with aqueous ethanol. This “organosolv”
lignin has a number-average molecular weight of less than
1000 and a polydispersity of 2.4–6.3. It is soluble in some
Chapter 12
organic solvents and in dilute alkali. This lignin may find
greater use in adhesives and resins than Kraft lignin. It has
been used as a reinforcing filler for poly(ethylene-co-vinyl
acetate).110 Any reaction that can use the phenol group is of
interest. One possibility is to demethylate lignin to a cate-
chol, which can then be reacted with a polyamine, possibly
an amine-rich protein, using an oxidative enzyme to form
the equivalent of mussel glue, the adhesive that holds the
mussel to the rock. This adhesive could cure under water,
for surgery or for boats. Demethylated lignin might also be
useful in the tanning of leather. The molecular weight of the
demethylated organosolv lignin will need to be raised for it
to be strong. This might be done by enzymatic polymeriza-
tion, by reaction with furfural or a bisoxazoline.
(Phenol–furfural resins are used to bond abrasive wheels
and brake linings.) Waste phenol–formaldehyde resin has
been liquified to liquid phenols in more than 95% yield by
hydrogenolysis in hot tetralin.111 This process should be
tried on organosolv lignin. Another route to “green phe-
nols” is the pyrolysis of softwood bark at 500°C, at 1.5
psi.112 This gave 30% oil (70% phenolic content), 29%
charcoal, 10% gas, and 31% water.
Lignin has been tested in blends with several different
polymers, including silicones, acrylics, polyurethanes,
epoxy resins, and polyvinyl chloride.113 Graft copolymers
of lignin with styrene are thermoplastic.114 IBM is using
lignin in its circuit boards. Sarkanen and co-workers have
prepared plastics containing 85% of nonderivatized Kraft
lignin by including polyvinyl acetate, diethyleneglycol
dibenzoate, and indene.116 They feel that such a mixture
could be extruded. They also report thermoplastic formula-
tions of 95–100% alkylated Kraft lignin. Earlier workers
have been able to put only 25–40% lignin into
polyurethanes, phenol–formaldehyde resins, epoxy resins,
acrylic polymers, and such. Lignin makes lignin–starch
composites more hydrophobic than starch alone.117
E. Proteins
Efforts to use proteins in plastics date back to the work of
Henry Ford on soybeans.118 The problems of these and
other protein-based films, fibers, and plastics include brit-
tleness, too much moisture absorption, and the need to
stabilize them against microbial degradation. Brittleness
can be due to a too low molecular weight, too much hy-
drogen bonding between chains, or too much cross-link-
ing. Plasticizers can be added to disrupt the hydrogen
bonding. Preferably, they should be polymeric, even
grafted to the protein, to avoid problems of leaching, mi-
gration, or volatilization. The addition of rubbers can re-
duce brittleness, provided that the phase separation of the
rubbery domains is in the proper form. The best ones in-
Materials for a Sustainable Economy 373

Spruce Ligin

12.24
Reprinted from E. Adler, Wood Sci. Technol., 1977, 11, 169–218 with permission of Springer Verlag and Chalmers Tekniska Hogskola.

volve a light grafting of the rubber to the parent polymer.
A polyurethane rubber, perhaps based on an oligomeric
ester diol, might be suitable for a protein. Strength can
also be increased by the addition of reinforcing fibers and
fillers. Cellulose or glass fibers might be suitable. The
molecular weight can be increased by some cross-linking.
The water absorption can be reduced by hydrophobic
groups added by grafting on a hydrophobic monomer,
blending in a more hydrophobic polymer, a hydrophobic
surface coating on the finished article, or other measures.
These methods are being applied to proteins with some
success. In the best cases, they involve additives derived
from renewable resources. Occasionally, these methods
can be used to produce edible films that extend food
life.119
Many potential new uses for soy protein and oil are be-
ing studied.120 Soy protein plastics plasticized with poly-
hydric alcohols, such as glycerol, ethylene glycol and
propylene glycol, are said to have the potential to compete
with engineering polymers if they can be kept dry.121
(Polyvinyl alcohol was not suitable as a plasticizer.122)
Films with tensile strengths of 2000 psi and 500% elonga-
tion can be blown from extrusion-blended soy protein and
30–40% of aliphatic polyesters.123 Although they are
brown and have a caramel-like odor, they may be suitable
for trash bags and mulching film. (For comparison, low-
density polyethylene trash bags have tensile strengths of
2000–3000 psi and elongations to break of 300–600%.)
Mixtures of zein (corn protein) or soy protein with
starch for extrusion or molding were cross-linked to in-
374
crease their tensile strength and water resistance.124 (Zein
treated with hot flax oil125 or oleic acid126 is also resistant
to water.) There is a surplus of corn protein as a by-product
of the conversion of corn to high-fructose corn syrup.127
The tensile strength of zein films plasticized with glycerol,
with or without polypropylene glycol, was increased two-
to threefold by cross-linking with formaldehyde or with
glutaraldehyde.128 The water vapor permeability went up
when the cross-linking agent was dialdehyde starch (made
by the oxidation of some of the pyranose rings with perio-
date). Zein fiber was cross-linked with citric acid or
1,2,3,4-butanetetracarboxylic acid using a sodium dihydro-
genphosphate catalyst.129 It had good stability to aqueous
acetic acid. Soy protein plasticized with glycerol and water
was spun, then finished with a combination of glutaralde-
hyde and acetic anhydride and oriented by stretching. It had
a water uptake of only 1.15%.130 Gelatin has been con-
verted to tough plastic films by cross-linking with 3% hex-
amethylenediisocyanate, followed by orientation by
stretching.131 The films swelled in water. A hydrophobic
surface treatment or coating would be needed for general
use. (Gelatin is obtained from the collagen in bones and
hides.)
Useful plastics have been made from the milk protein,
casein.132 The best ones were made using formaldehyde for
cross-linking. A more benign cross-linking agent would be
desirable. Sterilized edible films, with potential use in food
packaging, have been made by gamma-irradiation of casein
plasticized with propylene glycol or, better, triethylenegly-
col.133 An aqueous dispersion of modified, plasticized
wheat gluten was found to be a good film former.134 Films
of wheat gluten may be suitable for controlled atmosphere
packaging of foods because they have a high selectivity for
carbon dioxide over oxygen (28 at 24°C and 100% relative
humidity).135 The puncture resistance of films of cotton-
seed protein plasticized with glycerol increased on cross-
linking with formaldehyde, glyoxal, or glutaraldehyde.136
The grafting of vinyl monomers to proteins as a way to
improve toughness and resistance to water does not seem to
have been explored. Nor has the addition of rubbery parti-
cles been studied. The brittleness of polypeptides has been
exploited in a positive way in one case. The polypeptides
can be used in a chewing gum that can be easily removed
from hard surfaces because it becomes brittle on drying.137
Soy protein treated with alkali or the enzyme, trypsin, is
useful in adhesives.138 Plywood made with new modified
soy protein glues performs just as well as that made with
conventional phenol–formaldehyde resins.139
Chicken feathers can be converted to fibers for use in di-
apers.140 Each chicken produces 0.5–1.0 lb of feathers.
Feathers, hides, hoofs, and hair all contain proteins con-
taining cystine cross-links. Cured rubber containing disul-
Chapter 12
fide and polysulfide cross-links can be devulcanized by
heating and shearing with rubber chemicals, by ultrasound
and by microwaves.141 It can then be revulcanized. It
should be possible to prepare useful fibers and films from
feathers, hides, hoofs, and hair with the use of an ultrasonic
extruder. Molded objects might be made in a similar fash-
ion. The water resistance should be adequate, except per-
haps with feathers, where they could be made hydrophobic
by grafting or blending. If done properly, this might also
provide moth resistance for the shirt made from chicken
feathers. Birds oil their feathers by preening using the oil
from an oil gland. “Pleather,” a leather–fiber composite,
can be made from waste scraps of leather and hides by hot
pressing.142 Spider silk is very strong and resilient.143 The
dragline silk is five times as strong as steel (on a weight ba-
sis), twice as elastic as nylon, and waterproof. It is being
studied to see if polyamides with similar properties can be
made. A mutant Bacillus subtilis self-assembles to form
threads as long as 1 m that are as strong as steel on a weight
basis.144 If this can be scaled up, a promising biodegradable
fiber may be available for general use.
In a sustainable future, natural rubbers will be used
more and synthetic rubbers less. The epoxidation of natural
rubber can be used to extend the applications or rubber and
improve bonding.145
IV. POLYMERS FROM RENEWABLE RAW
MATERIALS197
A. Products from Polyols
Several approaches, both chemical and biological, are be-
ing taken to convert sugars, amino acids, and related com-
pounds to new polymers for commercial use.146 Glycerol
has been oxidized to a polymeric carboxylic acid (12.25)
that may find use in detergents to complex calcium ions.147
Propenyl ethers from glycerol and isosorbide (12.26)
are useful in photoinitiated cationic polymerization (e.g.,
for use in coatings).148
The polymerization is said to be fast with a low energy
input, is not inhibited by air, uses no solvents, is nonpollut-
ing, and uses inexpensive materials. The photopolymeriza-
tion of various epoxidized oils and terpenes also does this.
The propenyl ethers were made by isomerization of the cor-
responding allyl ethers with a ruthenium catalyst. The allyl
ethers were made from the hydroxy compounds with allyl
bromide and base, a process that produces waste salts. It is
possible that the monomers could be made by reaction of
the hydroxy compounds with propylene oxide followed by
dehydration so that no waste salts would be formed. Isosor-
bide is made by the acid-catalyzed dehydration of sorbitol,
in turn, obtained by the reduction of glucose.
Materials for a Sustainable Economy
12.25
12.26
Isosorbide has been reacted with acid chlorides of diba-
sic acids to form polyesters (12.27) with molecular weights
as high as 34,000 and melting points as high as 181°C.149
Many have lower molecular weights.
For use in plastics, this might require chain extension
with diisocyanates, bisoxazolines, carbodiimides, bis(an-
hydrides), and such. One use of the oligomers would be to
form polyurethanes by reaction with isocyanates. The use
of acid chlorides can be avoided if the polymers are made
by ester exchange or made enzymatically, with compounds
such as divinyl adipate. Poly(butylene sebacate) with a
molecular weight of 46,400 has been made has been made
from bis(2,2,2-trifluoroethyl)sebacate and 1,4-butane-
diol.150 One polyester with a molecular weight of 24,000
has been made by ester exchange from isosorbide and a
12.27
375
dimethyl ester (12.28), which can be derived from renew-
able sources (i.e., furfural and acetaldehyde).151 (Similar
polymers have been made using ethylene glycol as the
diol.152 Polycarbonates and polyurethanes have also been
prepared from isosorbide and other “sugar diols.”153
A variety of vinyl sugar monomers have been prepared
and polymerized.154 Many of the syntheses involve various
protecting groups. Probably, the most practical and direct
syntheses are those involving enzymatic formation of acry-
lates (as described in Chapter 9). This has been used to pro-
duce sucrose acrylate, as well as a monomer (12.29) made
from -methylgalactose and vinyl acrylate.
A copolymer of this monomer with N,N-methylenebis
(acrylamide) imbibed 100 times its weight of water. This
swelling was not affected by sodium chloride in the water.
Most “super-slurpers” swell less in the presence of dis-
solved salts. Thus, the new copolymer may be of use in col-
lecting urine in diapers. Another polymeric hydrogel was
made by polymerization of sucrose-1-acrylate using su-
crose-6,1-diacrylate (prepared by enzymatic transesterifi-
cation of sucrose and vinyl acrylate) as the cross-linking
agent.155
The monomer in (12.30) was made from glycerol, ace-
tone, and acetylene. The alternating copolymer with maleic
anhydride cross-links on standing in a moist atmo-
sphere.156 (The carboxylic acid that results from the action
of water on the anhydride catalyzes the cleavage of the ac-
376
12.28
12.29
etal. The remaining anhydride then reacts with the newly
formed hydroxyl groups.)
Epoxy resin adhesives for aluminum, glass, and steel
have been prepared by converting octaallyl or octacrotyl-
sucrose to the corresponding epoxides which were cured
with diethylenetriamine.157 Several plastics, resins, and ad-
hesives have been based on soybean oil.158 Vinyl esters of
the fatty acids can be used as monomers. The oil can be
epoxidized, then hydrolyzed to glycols, which can be con-
verted to acrylates or maleates for polymerization. Natural
fibers, such as hemp, can be used with such materials to
form inexpensive composites.
12.30
Chapter 12
B. Furfural
Many efforts have been made to base polymers on furfural
made from pentoses.159 The polymers may be useful, but
tend to have lower thermal stability than the usual synthetic
polymers. Polyesters based on furfural were mentioned
earlier. The acid-catalyzed polymerization of furfuryl alco-
hol is used in foundry cores.160 Furfural has been con-
densed with cardanol (m-pentadecadienylphenol) from
cashew nut shell oil in the presence of other phenols to pro-
duce polymeric resins.161 Cardanol and hydrogenated car-
danol have been polymerized with horseradish peroxidase
to soluble polymers in up to 85% yield.162 Plasticizers that
are effective in polyvinyl chloride, such as (12.31), have
been made from furfural.163
12.31
Materials for a Sustainable Economy
C. Polyurethanes
Renewable materials can be used in the preparation of
polyurethanes. Glycosides of polytetrahydrofuran have
been used with diisocyanates.164 Castor oil (which contains
about 2.7 OH per molecule) has also been used.165 Polyols
derived from epoxidized soybean oil have been used to
make polyurethanes.166 Lactic acid oligomers can be
used.167 “Wheat Board” is made from wheat straw and iso-
cyanates.168 It is said to be lighter and as strong as and more
resistant to moisture than conventional particle board. No
formaldehyde is needed for this building material.
D. Polyesters198
The production of poly(hydroxyalkanoates)169 by bacteria
was described in Chap. 9. They are being used in cups, cos-
metic bottles, water filters, and credit cards,170 but large-
volume applications will not develop until their prices are
more competitive with those of polyolefins. (Monsanto
abandoned development of them in 1998 as the costs re-
mained 25–50% above those of polyolefins.171) Inclusion
of wood fiber makes them cheaper and causes nucleation
that allows faster processing.172 They may find use in eco-
packaging because their barrier properties to carbon diox-
ide and water are reasonably good.173 One of their big sell-
ing points is their biodegradability.174 It allows them to be
recycled by composting.
Polylactic acid175 is also biodegradable, decomposing
relatively quickly under conditions in the body. This allows
it and related copolymers with glycolic and other acids to be
used in surgery, when something implanted in the body does
not have to be removed surgically.176 A prepolymer can be
made by heating lactic acid with a tin catalyst. This pre-
polymer can be extruded into fibers and films.177 Grignard
reagents have been used as polymerization catalysts to pre-
pare tin-free polymers.178 L-Lactide can be polymerized to
poly(lactic acid) in bulk without racemization using a zinc
lactate catalyst at 150°C.179 Aluminum isopropoxide can
also be used as the catalyst.180 The polymer is said to be suit-
able as commodity plastic for packaging, being similar to
polystyrene in many respects.181 The strength is increased
by orientation. When plasticized with varying amounts of
12.32
377
lactide (the cyclic dimer) or other oligomers of lactic acid,
its properties can mimic those of flexible polyvinyl chlo-
ride, low-density polyethylene, linear low-density
polyethylene, polypropylene, and polystyrene. It can also
be plasticized with 20% acetyltributyl citrate.182
E. Polyamides
Polyamides can be made from renewable resources in sev-
eral ways. Soybean-based dimer C36 fatty acids have been
polymerized with a variety of diamines, including 1,4-
phenylenediamine.183 Oxazolines, made from fatty acids
and ethanolamine (12.32) have been polymerized up to a
weight-average molecular weight of 148,000 with a poly-
dispersity of 3.4.184
Other chain lengths can also be used. Copolymers of
ones with long chains and ones with short chains have
been made. Some of these may find use as compatibiliz-
ers for polyamides. Poly(-stearyl-L-glutamate) has been
made by polymerization of the cyclic anhydride
(12.33).185
These amino acid anhydrides are usually made with
phosgene. The use of dimethyl carbonate should be tested
in the preparation of the monomers. Polyaspartic acid can
be made by heating aspartic acid without solvent to form a
polysuccinimide which is then hydrolyzed (12.34).186 It
can also be made directly from maleic anhydride and am-
monia. It promises to be useful as a scale inhibitor in water,
an antiredeposition agent in detergents, and such. Gamma-
irradiation converts it to a biodegradable superabsorbent
material that takes up 3400 g water per gram of dry poly-
mer.187 (Most superabsorbent polymers are based on acry-
lamide, a neurotoxin.)
Poly(-glutamic acid), an analogue of poly(aspartic
acid) with another methylene group in the side chain
(12.35), is produced by Bacillus subtilis.188 (Notice that
polyglutamic acid made by chemical synthesis involves the
other carboxylic group.) Esterification improves the pro-
cessibility and the solubility in organic solvents.
Adipic acid and hexamethylenediamine have been
copolymerized with 37.5–47.5 mol% of proline, alanine, or
glycine to produce polyamides with number-average
molecular weights of about 20,000.189 They have been sug-
378 Chapter 12

12.33

12.34

gested for use as biodegradable food packaging. Their cost

could be reduced if mixed amino acids from the hydrolysis
of waste protein could be used. It might also be possible to
pass a mixture of adipic acid, hexamethylenediamine, and
waste protein through a vented extruder to make such prod-
ucts. Polyamides with molecular weights up to 26,700
(12.36) have been made from the benzyl ester of lysine and
activated diesters of dicarboxylic acids.190 Tyrosine-based
polycarbonates have also been made.191
Thermally reversible polymers might make recycling
12.35 easier. Some brittle ones have been based on sorbic acid,
lysine, glycine, and maleic anhydride (12.37).192 The poly-
mers form by the Diels–Alder reaction.

12.36
Materials for a Sustainable Economy
12.37
12.38
A furan ester has been used in a similar way at 60°C
with another bismaleimide (12.38) to make polymers with
molecular weights as high as 30,000.193 The problem is that
Diels–Alder adducts of furans reverse at relatively low
temperatures, in this case at 90°C or more. Such polymers
would have to be used at room temperature or not much
higher.
V. CONCLUSIONS AND
RECOMMENDATIONS
There are ways to make many of the major polymers used
today from renewable raw materials. Many of the synthe-
ses will require further study and optimization before they
can be used commercially. The economics will change
with the shift to the new raw materials and what is inex-
pensive now may not be after the change. It may be less ex-
pensive to use the natural polymers again. As many of these
have been given little attention since the advent of cheap
petroleum and natural gas, further study using the addi-
tional knowledge and methods available today is indicated.
This should include new methods of fabrication, new
chemical derivatives of natural polymers, bonding agents
for fillers, compatibilizers for polymer blends, polymeric
plasticizers, surface coatings as barriers for gases and liq-
uids and for scratch or hardness resistance; methods of
379
graft polymerization and ways of upgrading present day
wastes to the status of valuable coproducts. By gaining a
better understanding of natural polymers, such as spider
silk and mussel glue, it may be possible to prepare valuable
new materials from renewable raw materials. Such re-
search may hasten the change from products based on
petroleum and natural gas to those based on materials from
forests and fields, especially if methods can be found to
make products from the latter less expensive.
The biggest unsolved need is to find a way to curb the
overconsumption of material goods by the developed na-
tions.194 There must be a way to shift back from single-use,
throwaway items to reusable ones. Chapter 13 will cover
ways to make things last longer. Ways must be found to re-
cycle the materials in items that are worn out over and over
again, instead of just burning them for their energy content.
Recycling will be covered in Chap. 14. All of this must be
done with much less energy than is used today, because it
will have to come from renewable sources, as described in
Chap. 15.
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RECOMMENDED READING
1. B.Y. Tao, Chem. Ind. (Lond.), 1994, 906 [industrial products
from soybeans].
2. D.J. Murphy, Chem. Br., 1995, 31(4), 300 [oleochemicals].
3. J.N. BeMiller, Kirk–Othmer Encyclopedia of Chemical
Technology, 4th ed., 1992, 4, 932–938 [cellulose, hemicellu-
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4. M.A. Colgin and R.V. Lewis, Chem. Ind. (Lond.), 1995,
1009 [spider silk].
5. E.M. Kirschner, Chem. Eng. News, Apr. 8, 1996 [top 50
chemicals].
EXERCISES
1. Devise a way to make benzene from renewable ma-
terials. Look up the major uses of benzene. Because
it is a carcinogen, can we do without it in a sustain-
able future?
2. What chemical reactions could be run on soy or
corn protein to decrease brittleness and water ab-
sorption? Can you devise a system to do this with
reagents from renewable sources for use in a twin-
screw exruder?
3. Choose a food-processing waste. How could some-
thing useful be made from it? If you cannot think of
one, try chicken feathers.
4. Cutin is a material on the surfaces of leaves and
fruits that keeps the water in and the rain out. What
food-processing wastes might be used as its source
for putting a hydrophobic coating on molded pro-
tein products? Outline the steps to do this.
5. What reactions could be run on the lignin from the
pulping of wood with aqueous ethanol to upgrade it
for large-scale applications.
6. Knowing that sulfonation of aromatic compounds
is a reversible process, can you think of a way to re-
move the sulfonate groups from Kraft lignin? The
product would be an analogue of “organosolv”
lignin.
13
Chemistry of Longer Wear
I. WHY THINGS WEAR OUT
The first step in achieving longer wear is to replace throw-
away items by reusable ones. Even the reusable ones will
wear out eventually. If the process is understood, it may be
possible to intervene by altering the design or manner of
use so that a longer service life is obtained.
Metals can rust or corrode. Rubber can harden and crack
with age. Plastics may embrittle with age. Colors may fade
in the sunlight. These are due to oxidation. Efforts to min-
imize these processes involve isolation of the object from
the environment, by a coating or other means, or by the use
of additives that prevent the oxidation. Concrete may dete-
riorate under the influence of deicing salts. Other objects
wear out mechanically. A cutting edge becomes dull. The
knees of the pants wear through from abrasion. Stockings
snag and rip. Teeth come out of zippers. Plastics may
scratch or stain. The rung on the chair may break. Glass and
china objects may break if they are dropped or hit. Some
plastics are brittle on impact. Biological factors may also
be involved. The clothes moth likes to eat woolen gar-
ments. Water-based paints, inks, cutting fluids, and such,
may serve as substrates for the growth of bacteria and
fungi. Termites and carpenter ants may eat the wood in
houses. Understanding the ecology of these organisms can
sometimes provide means to prevent their entry. Other-
wise, biocides are used.
There is often a weak link in an appliance or piece of
equipment. A plain steel screw in a stainless steel pot will
fail first. The screw is used because stainless steel is harder
to machine. A plain steel knife keeps its cutting edge better
than one made of stainless steel. A small spring may fatigue
and break. A nut may be lost from a bolt. Many nuts are
locked on by putting a monomer on the threads which then
polymerizes when no more oxygen is present.1 This is an
387
anaerobic adhesive. The important thing is for the equip-
ment to be designed for ease of disassembly for easy re-
placement of the weak link. This will require more screws
and fewer rivets, welds, and metal parts encased in plastic.
It may require more standardization of sizes of screws or
other parts. The second factor is that the spare part should
be easy to obtain, preferably locally. A generation ago it
was possible to buy the one screw needed at the neighbor-
hood hardware store. Today, one may have to drive to a
mall and buy a prepackaged assortment of two dozen
screws. It may be best if the owner can replace the part him-
self. The next best option would be a local repair service.
For more complicated equipment, shipment to a central re-
pair facility might be necessary. Generators for automo-
biles are handled in this manner. Other weak links include
the elastic thread in underwear that fails long before the
cloth, and the holes that develop in pockets long before
they form anywhere else in the pants. Ideally, the weak link
would be redesigned so that it is no longer weak. This may
require chemists to devise new and better materials.
Some of the failures can be due to improper use of the
object or lack of preventive maintenance. Running without
coolant will damage some machinery (e.g., a car). Storing
a steel bicycle or shovel outdoors will encourage rusting.
An item of polyethylene would melt if put in the oven.
Plain glass might crack in the oven, whereas Pyrex glass
would not. Glasses may etch in the dishwasher over time if
the detergent is too alkaline. Making the china mug thicker
than the delicate teacup reduces breakage. Putting wet ob-
jects directly on wooden furniture may ruin the finish. This
can be avoided by using furniture with tops of
melamine–formaldehyde resin laminates. Shovel handles
may break if used for prying. The cutting edge on the saw
will be dulled if one tries to saw through wood with nails in
it. A small rung on a chair may break if someone steps on
388
it. Torque wrenches were devised to prevent the applica-
tion of too much force to nuts and bolts.
Some of the failures are due to the improper choice of
materials or poor designs. The cutting edges on saws,
planes, chisels, knives, and such will stay sharp longer if
they are made of a good tool steel. They should be easy to
resharpen. The spring will last longer if it is made of a good
tool steel and not overextended in use. It is easy to cast
“white metal,” but the castings tend to be somewhat brittle
and often break with time. A household strainer of stainless
steel will last longer than one made of plain steel. Stainless
steel knives, forks, and spoons will hold up better than
those plated with silver, and there is no tarnish to be taken
off. Chutes and trucks carrying rocks will last longer if they
are lined with rubber or with ultrahigh molecular weight
polyethylene.
A ceramic may not have been fired hot enough. Furni-
ture, plywood, and particle board not made with waterproof
glue should not be put into exterior use. The galvanized
coating on wire or gutters may not be thick enough to
weather well. Gutters of aluminum, copper, stainless steel,
and plastic avoid this problem. Furniture drawers made
with dovetailed joints will hold together longer than plain
ones just nailed or stapled together. A floor made of oak
will wear less than one made of pine.
Coatings containing pinholes fail sooner than others. A
better coalescing agent for water-based paints may be
needed. Coatings may not adhere well to substrates that
have not been sanded. The coating may not adhere well if
it has not been designed for the substrate in question. This
can be a problem for inks for polyolefins, which lack
functional groups. The usual practice is to treat poly-
propylene film with a corona discharge to put some oxy-
gen-containing groups on the surface. Paper sized under
acidic conditions embrittles with age, but paper sized un-
der neutral conditions lasts much longer and is specified
for archival use. Neutral sizing also permits better recy-
cling of water in the plant. A natural wood finish on a
home may have to be redone every couple of years. An
oil-based paint would last two to three times longer. If the
home were built with aluminum or plastic siding, or fin-
ished in stucco, brick, or stone, this periodic recoating of
the surface would be unnecessary. Roofs made of slate or
tile last longer than those made of asphalt shingles. Dyes
and pigments that are not resistant to light should not be
used in objects to be used outdoors or even next to the
window in the living room.
Stockings and panty hose would last longer if they were
made of rip-stop nylon, a woven fabric. Making them
thicker would also help. Rotating the rug or moving the fur-
niture once in a while, so that the wear will be in different
places, will make the rug last longer.
Chapter 13
A great many useful objects are made of plastics. The
preferred methods of fabrication of many plastics involve
melting the plastic and putting it into a mold or forcing it
through a spinneret to form a fiber. If this process is done
at too high a temperature, the polymer or the additives in it
may be degraded. The extra heat is usually applied in an ef-
fort to speed up the line. As the molecular weight goes up
so does the viscosity and the strength. To obtain the maxi-
mum strength, the molecular weight should be high enough
to be on a plateau where no further increase in the one will
affect the other. The usual molding conditions are a com-
promise between optimal strength and a viscosity that can
be handled in the equipment. Adding ultrasound to an ex-
truder can raise the molecular weight above that which can
be processed without it. Ultrahigh molecular weight
polyethylene (molecular weights of 1 million or more) can-
not be processed by these methods. However, when fiber is
prepared by a solution method, the fiber is strong enough to
be used in bulletproof vests. Further research on cross-link-
ing or chain extension during fabrication may lead to
stronger, tougher parts. On the other hand, too much cross-
linking can lead to hard, brittle objects. The glass transition
temperature is also important. If a rubbery polymer is used
below its tg, it will be rigid instead of rubbery. If a plastic
is used above its tg, it will gradually change its size or
shape, a process termed creep.
The additives to the polymers make a world of differ-
ence.2 A brittle polymer, such as polystyrene, can be made
to resist impact by inclusion of little rubber balls a few mi-
crons in size. The rubber diffuses and dissipates the force
that hits the object. The trick is to find a way to make the
rubber separate in the proper manner during fabrication.
The best method involves light grafting to the preformed
rubber during polymerization of the other monomers. Pre-
formed rubber particles of the core-shell type have been
used to toughen acrylic polymers.3 The same principle ap-
plies to the macroscopic particles of rubber that make as-
phalt pavements last longer (see Chap. 14). Reinforcing
fibers and fillers can increase strength. The lifetimes of au-
tomobile tires have been increased greatly in the past 20
years by switching to a radial design of the belts and using
reinforcing silica fillers in poly(1,3-butadiene) treads.127
The carcass is often made of a different rubber (e.g., a
copolymer of styrene and 1,3-butadiene). Shoe heels are a
different story. They are made of highly filled reclaimed
rubber. If they were made the same as tire tread, wear
would not be a problem.
The useful lives of some polymers are determined by
how long the plasticizers and stabilizers remain in them.
Losses by volatilization, migration, and leaching are great-
est for thin sections, such as fibers and films. The plasticizer
in the polyvinyl chloride seat covers in a car volatilizes and
Chemistry of Longer Wear
condenses on the inside of the windshield. It is responsible
for the smell of a new car. The seat covers become less flex-
ible as the plasticizer leaves. The use of plasticizing
comonomers, such as vinyl stearate, or polymeric plasticiz-
ers can obviate the problem of plasticizer loss. The use of
newer polyolefins, with the properties of flexible polyvinyl
chloride, instead of polyvinyl chloride itself will eliminate
the problem of plasticizer loss (see Chap. 12). The problem
with the elastic natural rubber “cut” thread in the underwear
may be twofold. The stabilizers may come out in the wash,
allowing the unsaturated polymer to oxidize more readily.
Grafting of the stabilizer to the polymer may also be possi-
ble. This may be the wrong rubber to use. The choice of a
less unsaturated rubber, such as polyisobutylene or a
polyurethane, might solve the problem of the elastic thread
in the underwear. Some plastics are not stabilized ade-
quately. Because the stabilizers usually cost several times
as much as the polymer, there is a tendency to skimp on the
amounts used. The “general-purpose grade” should not be
used for any demanding applications.
II. STABILIZERS FOR POLYMERS
Plastics fail for a variety of reasons.4 Cellulose nitrate film
in museum collections is failing owing to release of nitric
acid.5 The degree of degradation is related to the amount of
sulfate left in the sample when it was made. Polyvinyl chlo-
ride objects fail from loss of plasticizer and from loss of hy-
drogen chloride. Polymers with ester backbones may be
subject to hydrolysis in use. The most common type of
degradation is oxidation, both thermal and light-catalyzed.
Any of these processes that lower the molecular weight be-
low that needed for adequate strength will limit the useful
life of the polymer. On the other hand, there a few places
for which controlled degradation is desired (e.g., agricul-
tural mulch, litter, and surgical sutures). Transition metal
dithiocarbamates can be added to the first two to give time-
controlled photolysis.6 (For polyesters used in the third ap-
plication, see Chap. 12.)
Polymer stability varies greatly. Polymethyl methacry-
late, bisphenol polycarbonate, and polyvinyl fluoride last
for many years of outdoor exposure. The first two can be
used for unbreakable windows in buses, schools, and else-
where. The problem is that they become scratched. A
13.1
389
highly cross-linked scratch-resistant coating is put on auto-
mobile headlights of these polymers by radiation curing.
Polyvinyl fluoride can be used to coat the exteriors of
buildings. Polyurethanes made with aliphatic isocyanates
are more stable outdoors than those made with aromatic
isocyanates. The latter absorb more ultraviolet light. Poly-
olefin polymers are subject to oxidation. Polypropylene
and poly(1,3-butadiene) could not be used commercially
without the addition of stabilizers. A trace of antioxidant is
added even before the workup of these polymers when they
are made. The radicals formed from these polymers are sta-
bilized by being tertiary in the first case and being allylic in
the second case (13.1).
Polyethylene, which lacks the many branches, is more
stable, but still requires the addition of stabilizers. Poly-
isobutylene, which is a saturated rubber, is more stable than
the unsaturated rubbers. Polymethyl methacrylate, in
which oxidation would have to produce a primary radical,
is much more stable. Polyamide degradation begins with
abstraction of a hydrogen from the methylene group next to
the nitrogen atom, giving a radical that can then react with
oxygen.7
A wide variety of stabilizers are used in plastics and rub-
bers.8 It is common for more than one to be used in a given
polymer. The total amount added, for example, to
polypropylene, is usually under 1%. Because the stabilizers
are used up in protecting the polymer, more may have to be
added when used items are recycled by remolding.9 Oxida-
tion of a hydrocarbon is a chain reaction (13.1).
R•  O2 → ROO• RH
 → ROOH  R•
ROOH  Mn → ROO•  M(n1)  H
ROOH  M(n1) → RO•  Mn  OH
RO•  RH → ROH  R• (13.1)
The initiating radical may be formed by mechanochemical
scission during molding10 or by ozone in the air.128 If a
metal ion that can have multiple valences is present (e.g., a
trace of iron from the extruder), the oxidation can be accel-
erated. In the case of polypropylene, a new radical and,
hence, a new hydroperoxide can be formed by backbiting
(13.2).
An alkoxy radical, formed as peviously mentioned, can
cleave the chain to form a ketone. The primary radical
390
13.2
would promptly abstract a hydrogen atom from something
to form a tertiary radical. The extent of degradation of
polypropylene is sometimes estimated by measuring the
carbonyl content by the infrared spectrum of the sample. If
light is present, the ketone can undergo further cleavage.
Antioxidants11 interrupt these chains by forming radi-
cals that are too weak to abstract hydrogen atoms from car-
13.3
13.4
Chapter 13
bon atoms. These radical scavengers contain hydrogen
atoms that are easily abstracted. The most active are aro-
matic amines12 such as those in 13.3.
The radicals formed are stabilized by electron delocal-
ization in a number of resonance structures, some of which
are shown in 13.4.
These are staining antioxidants owing to the imine
Chemistry of Longer Wear
13.5
structures that can form. Abstraction of a second hydrogen
atom would lead to highly colored quinone imines. The di-
hydroquinoline cannot do this and is classed as semistain-
ing. Staining antioxidants can be used when the color does
not matter, as in gasoline and black rubber tires. Ozone
causes cracking in rubber under stress. The cleavage of car-
bon–carbon double bonds by ozone is well known. Antio-
zonants tend to be of the aminodiphenylamine type.13
Waxes that bloom to the surface are used to limit the entry
of ozone.
13.6
13.7
391
The less active hindered phenols are used in most plas-
tics to avoid the staining. The simplest, and perhaps cheap-
est, is 2,6-di-tert-butyl-4-methylphenol. Abstraction of
hydrogen leads to a resonance-stabilized radical (13.5) that
cannot abstract a hydrogen from a carbon atom owing to
steric hindrance and low reactivity.
Although this phenol can be used in gasoline, it is too
volatile for use in most plastics, especially in thin sections,
as in fibers and films. For these uses, analogues of higher
molecular weight, such as the ester of pentaerythritol
(13.6), are used.
The hydroperoxides formed in the oxidation can be de-
composed by the use of S(II), S(IV), or P(III) compounds.
A few peroxide decomposers are shown in 13.7.
ROOH  S(CH2CH2COOC18H37)2 →
ROH  O 
 S(CH2CH2COOC18H37)2 (13.2)
The cyclic sulfite is derived from a hindered phenol.14 Be-
cause the antioxidants and peroxide decomposers operate
by different mechanisms, they are synergistic and are often
used together (13.7).
392
13.8
The rate of degradation increases when polyolefins are
used around copper wire. Copper is also undesirable in
gasoline. Metal deactivators are used in these cases.
The oxalylhydrazone probably forms a metal complex
that is too insoluble to act as a catalyst for oxidation. The
propylenediamine derivative is used as a metal deactivator
for gasoline. It may work by changing the redox potential
of the copper. Talc accelerates the rate of loss of mechani-
cal properties when used as a nucleating agent for
polypropylene.15 This may be due to traces of transition
metal ions in the mineral. Metal-containing pigments
sometimes behave in the same way. It might also be due to
adsorption of stabilizers on to the talc.16 Citric acid and
ethylenediaminetetraacetic acid (EDTA) are food-grade
metal deactivators for use in systems more polar than hy-
13.9
Chapter 13
drocarbons (13.8). Citric acid is good for deactivating
iron(III).
Additional measures have to be taken when light is in-
volved in the degradation of the polymer.17 Electrolumi-
nescent polymers have been encapsulated in resins to keep
oxygen and water out and prevent degradation by singlet
oxygen.18 Use of carbon black as a pigment also keeps light
out and prevents photodegradation.19 Ultraviolet screening
agents can also be used to keep the light out. Two types
work by photoenolization (13.9), which allows the energy
to be dissipated as heat without harming the polymer.
Typically, R and R are long alkyl chains that make the
compounds more soluble in polyolefins.
Excited states can be quenched by metal chelates, such
as 13.10 (which has a light green color).
Chemistry of Longer Wear 393

The best light stabilizers are the hindered amines. A typ-

ical one is shown in 13.11. They are used along with the an-
tioxidants and peroxide decomposers. Their exact mecha-
nism seems to be a matter of debate. One mechanism is
shown (13.11).20
Thus, each molecule destroys more than one radical
chain. A variety of analogues of higher molecular weight,
often oligomeric polymers, is available commercially for
use in fibers and films, where the one shown (see 13.11)
might be too volatile.21 Another method that has been used
13.10 to reduce volatility is to react a hindered piperidinol or
aminopiperidine with a graft copolymer of maleic anhy-
dride on polypropylene to form an ester and amide, respec-
tively (13.12).22
A hindered amine monomer has been grafted to
polypropylene in the presence of a peroxide at 200°C.23
Grafting the hydroxybenzophenone monomer (13.13) to
wood stabilized the surface to light, whereas a monomeric
equivalent did not.24

13.11

13.12
394
13.13
The hindered amine and a peroxide decomposer have
also been combined in one molecule (13.13).25
A product made by grafting a mixture of styrene and
vinyltrimethoxysilane on to EPDM (ethylene–propy-
lene–diene monomer terpolymer rubber) was able to re-
place ABS (acrylonitrile-1,3-butadiene–styrene terpoly-
mer).26 The product showed improved heat and light
stability by the removal of the unsaturation. The need to use
the carcinogenic acrylonitrile was eliminated.
Acid acceptors are used when acids may be involved in
the degradation of the polymer. Calcium stearate is often
used with polypropylene to neutralize any mineral acids,
such as hydrochloric acid, that might result from the reac-
tion of water with catalyst residues. Various mixed metal
laurates are used as stabilizers in polyvinyl chloride. Ef-
forts are underway to replace the cadmium in some of these
mixtures (see Chap. 4). Epoxidized soybean oil has been
used as the acid acceptor, along with dioctyltinbis(thiogly-
colate), to improve the heat stability of polyvinyl chlo-
ride.27
13.14
13.15
Chapter 13
Synthetic antioxidants, such as 2,6-di-tert-butyl-4-
methylphenol are not allowed in foods in Japan. In the
United States they can be used in the wrapper around the
cereal in small amounts, but not in the cereal itself. There
is great interest in natural antioxidants that can be used to
protect foods.28 That these natural phenols from plants may
scavenge free radicals in the body and, thereby, reduce the
incidence of heart attacks and cancer makes them espe-
cially important. Vitamin E (13.15) is the one that we must
all have in our diets.
Some synthetic analogues (13.16) show higher activity
than vitamin E.29
The naphthalene unit presumably allows enhanced elec-
tron delocalization to form a more stable radical. Plant fla-
vanoids can be good antioxidants. Luteolin is a better an-
tioxidant than 2,6-di-tert-butyl-4-methylphenol.30 Green
tea is a good source of antioxidant flavanoids, one of the
13.16
Chemistry of Longer Wear
13.17
most active being epigallocatechin gallate (13.17).31 It may
act by inhibiting the enzyme urokinase (in cases where it
causes the reduction of the size of tumors).32
A wide variety of extracts of plants and spices have also
shown antioxidant activity, often comparable with or better
than that of 2,6,-di-tert-butyl-4-methylphenol.33 These in-
clude the phenols in extracts of rosemary,34 black pepper,35
buckwheat,36 peanut hulls,37 and others.38
III. LUBRICATION, WEAR, AND RELATED
SUBJECTS
If two objects are rubbed together, they may wear by abra-
sion. The heat developed in the process may cause them to
deteriorate by oxidation, loss of strength, or they may melt.
In fact, this is one way to weld two pieces of plastics to-
gether. They are rotated against each other until the surfaces
melt together, then removed from the apparatus to cool. A
lubricant39 lowers the coefficient of friction allowing one
surface to slide over the other more easily without, or with
less, abrasion. It can also, when passed through continu-
ously, cool the surfaces and remove any particles that form.
There are some special cases for which it is unnecessary
to add a lubricant. Magnetic bearings and bearings that are
suspended by a pressurized gas have no metal-to-metal con-
tact so that wear and heat buildup are avoided. Several com-
panies sell oil-free vacuum pumps that eliminate the trouble
and expense of changing the oil, disposal costs, and con-
tamination of process chambers, which is especially impor-
tant in the manufacture of semiconductors and liquid crys-
tal crystal displays.40 Plastic gears of nylon or
polytetrafluoroethylene are self-lubricating and need no
added lubricant. They reduce the noise associated with ma-
395
chinery. They may be made with graphite or molybdenum
disulfide in them as additional built-in lubricants. These are
layered substances where the layers tend to slide over one
another easily. Copper particles,41 glass fibers, carbon
fibers and such in polytetrafluoroethylene also reduce
wear.42 A small amount of silicone oil (1.5–2.0%) in a ther-
moplastic polyurethane improved its wear characteristics.43
Polyetheretherketone has a lower coefficient of friction and
wear rate when 7.5%-nm–sized zirconia is included in it.44
Films of carbon deposited from a radiofrequency plasma of
argon have a coefficient of friction of 0.001, which is 20
times lower than that of molybdenum disulfide and 40 times
lower than polyterafluoroethylene.45 If a way can be found
to apply them to large objects, they should be tried to pre-
vent the fouling of pipes and ships by marine organisms.
As mentioned earlier in this chapter, wear can some-
times be reduced by putting a coating of polyurethane rub-
ber or of ultrahigh molecular weight polyethylene on a
metal surface. Sometimes, wear can also be reduced by
making the surface harder. Cross-linked coatings on the
surfaces of plastics can do this. The wear of high-density
polyethylene was reduced by a thin surface film made by
plasma polymerizing a mixture of acetylene, hydrogen, and
silane.46 Harder surfaces were produced on polymethyl
methacrylate by transamidation with diamines.47 Another
way to do it is to deposit a transparent layer of silica or ti-
tania by the sol–gel method. High-energy ion irradiation
can be used to make the surfaces of common polymers,
such as polyethylene, poly(ethylene terephthalate),
polystyrene, nylon, and others, harder than steel.48 This
might provide a way to eliminate the scratching and stain-
ing of plastic dinnerware made of melamine–formaldehyde
plastics. Another possibility would be to apply a diamond
396
coating by the three-laser method.49 Diamonex Co. offers
amorphous and polycrystalline diamond coatings (pre-
pared by chemical vapor deposition50) that increase the
wear of plastics, glass, and metals.51 These coated objects
would also offer an advantage over glass and ceramic din-
nerware in not breaking when dropped.
Face materials for seals can be made of carbon–
graphite, silicon carbide, tungsten carbide, or alumina.52
The last three do require lubrication. Cutting tools with
tungsten carbide tips or diamond coatings are common.
Metal surfaces may also be hardened by carburizing, nitrid-
ing, or metallizing with a metal with greater lubricity or
hardness (see Chap. 4). Thin films of titanium nitride, tita-
nium carbide, alumina, (5 m), which extend tool life 4–20
times, have been deposited by chemical vapor deposition,53
magnetron sputtering, and pulsed direct current sputter-
ing.54 Multilayered coatings of TiN/VN and TiN/NbN were
even harder. Clear multilayered films of Al2O3/ZrO2 should
be able to protect a wide variety of objects without the use
of any toxic metal ions. Small amounts of silicon and tita-
nium make an alloy of aluminum, magnesium and boron
slightly harder than boron nitride at one third of the cost.129
The hardness and resistance to wear of aluminum alloy
quasicrystals, such as Al65Cu23Fe12, may make them suit-
able as protective coatings for engine parts and other appli-
cations during which sliding motions can cause abrasion.55
They can be toughened by inclusion of some iron alu-
minide. Ceramics, which are normally brittle, can be made
less so if their grain size is reduced to the nanometer range56
or if layered structures are used.130 Epoxy resins containing
10% of 32-nm particles of titanium dioxide were more re-
sistant to cracking under strain and to scratching than either
the unfilled resin or when the resin was filled with the usual
microparticles of titanium dioxide. Nanocomposites of ny-
lon containing a few percent of 1-nm–thick platelets of clay
were stiffer, stronger, and just as tough as the unfilled nylon.
Ceramics can be made tougher by inclusion of ceramic
fibers.57 Fibers of amorphous Si-Al-C-O material58 and
SiBN3C59 are suitable for use in air up to 1500–1600°C,
whereas those of crystalline SiC cannot be used above about
1300°C because of loss of mechanical strength above this
temperature. These fibers are prepared by firing fibers spun
from polymeric precursors, as in 13.18.
Ceramics reinforced with such fibers may increase the
energy efficiency of engines by allowing them to run as
13.18
Chapter 13
higher temperatures. A ductile ceramic consisting of an in-
terpenetrating network of single crystals of alumina and
single crystals of gadolinium aluminate (GdAlO3) has been
made by unidirectional solidification of a eutectic mixture
of the two materials. It shows high strength and metal-like
pliability at up to 1600°C.60 Sodium aluminosilicate glass
can be made up to five times stronger by exchanging potas-
sium ions for sodium ions in the surface, then back-ex-
changing with sodium ions.61 Samples fail safely by multi-
ple cracking. (The safety glass in automobiles, which
cracks in a similar fashion, consists of two sheets of glass
with a layer of poly(vinyl butyral) between them.)
Most lubricating oils are based on petroleum.131 For opti-
mum results, numerous additives are required. These include
antifoaming agents (typically silicone oils), antioxidants,
corrosion inhibitors, detergents or dispersants, metal deacti-
vators (such as zinc dithiocarbamates or dithiophosphates),
pour-point depressants (such as a polyalkyl methacrylate),
viscosity index improvers (such as ethylene–propylene
copolymers, hydrogenated diene–styrene copolymers, or a
polyalkyl methacrylate [from C4,C12,C18 methacrylates]).
Pour-point depressants lower the temperature at which the oil
can be used (e.g., needed in engine oil in parked cars in the
winter). They prevent wax from crytallizing out in a form that
would interfere with the functioning of the engine. Viscosity
index improvers62 reduce the amount of the decrease in vis-
cosity as the oil heats up. Extreme pressure lubricants, as
needed for gears, use phosphorus or sulfur compounds, such
as sulfurized polybutene and zinc dialkyldithiophosphates.
As one part slides over another, these compounds produce lu-
bricating layers of metal sulfides or phosphides on the metal
surfaces.132 The zinc dialkyldithiophosphate also functions
as an inhibitor for corrosion and oxidation. Greases are made
by adding 4–20% of a metal (usually lithium or calcium)
fatty acid soap to an oil to thicken it. Inorganic thickeners,
such as silica and montmorillonite (a clay), can also be used.
Used engine oils can be reused. Sometimes, all that is
needed is removal of particles by filtration or centrifuga-
tion. In others, it may be necessary to remove volatile acids
and water by heating, followed by treatment with sulfuric
acid, then lime, and, sometimes, bleaching clay. A final
distillation under vacuum completes the rerefining.63 An-
other system uses propane at ambient temperature in a con-
tinuous process.64 The additives and impurities precipitate
and settle out, after which the propane is flashed off and the
Chemistry of Longer Wear
oil distilled. A new package of additives is usually required
before reuse. A company in Florida reports an “electric mo-
bile oil refiner” that can extend the life of motor oil “indef-
initely”.65 Texaco offers an on-site mobile reclamation and
refortification service for lubricants.66
Synthetic oils67 are used for more demanding applica-
tions, such as use at higher temperatures. Esters of pen-
taerythritol [C(CH2OCOR)4, where R averages about C7]
are often used at higher temperatures. Phosphate esters,
such as tri(o-tolyl)phosphate, and silicone oils are also used
at higher temperatures. Silicone grease is made by dissolv-
ing a lithium soap in a silicone oil. Solid lubricants, such as
the layered materials graphite and molybdenum disul-
fide,133 are used for extreme conditions of temperature or
chemical resistance. Hollow nanoparticles of tungsten
disulfide outperform these materials and may come into
common use.68 They are made by treating hollow nanopar-
ticles of tungsten(VI) oxide with hydrogen sulfide and hy-
drogen at 800–850°C.
High-oleic vegetable oils can be used in place of mineral
oils69 (see Chap. 12). They can also be used as hydraulic
fluids. They can be used as food-grade lubricants, are from
renewable sources, and are biodegradable, which helps if a
spill occurs. Additives are also required for these oils.
Ethanolysis of such oils would produce ethyl oleate for use
as fuel with the same diesel engine that uses the oils for lu-
brication and in its hydraulic lines. Oligomeric esters of
oleic acid, formed by self-addition of the carboxylic acid
group to the double bond in the presence of a sulfuric acid
catalyst, can also be used as biodegradable lubricants.70
Cutting oils are used in metal working to cool the work-
piece and the tool, to lubricate and to remove the cuttings.
These can be water-based, as in an emulsion of 2–5% min-
eral oil with added antifoaming agent, biocide, and corro-
sion inhibitor. They can also be based on polyalkylene gly-
cols plus fatty acids, stabilizers, biocide, corrosion
inhibitor, and such, without any mineral oil.71 Tri-
ethanolamine salts of ricinoleic acid polymers or of the half
esters of C36 dimer fatty acids are suitable corrosion in-
hibitors for water-based cutting oils.72 The emulsions con-
taining oil can be recycled on site in a unit that can be mo-
bile.73 The process involves filtration, pasteurizing,
centrifugation, and addition of more additives. The use of
hollow-fiber membranes to transport the oil and reject the
water in cutting oils has also been studied.74 Monsanto has
developed a protein-based metal-working fluid.75 Re-
cently, it has been found that coating a tungsten carbide
cutting tool with a nanolayer of tungsten plus tungsten
disulfide eliminates the need for a cutting oil. It also allows
the tool to be designed with sharper edges, which reduces
the force on it by a factor of two to three.76 This helps re-
duce the amount of heat generated. (Laser machining also
397
eliminates the need for a cutting oil.77) Diamond coatings
can be used on tools also, but not for cutting steel, since for-
mation of iron carbides destroys the coatings.78 The prob-
lem of a thermal mismatch (i.e., the coating expands at a
different rate than the substrate on heating) that can pro-
duce delamination and cracking of the diamond film has
been solved by creating a “three dimensionally thermally
and compositionally graded interface”.79
Grinding fluids may be a 2% emulsion of oil in water.
Without such a coolant, enough heat may be generated to
damage the workpiece. Studies are being done to eliminate
the fluids by the use of liquid nitrogen as the coolant.80 An-
other system uses minute amounts of a nonhazardous ester
oil applied by a microlubrication system plus a jet of cold
air.81 Perhaps, the particles in grinding wheels can be re-
designed with the new tungsten–tungsten disulfide coat-
ings, mentioned earlier, for tools. Sharper particles would
reduce the heat generated in grinding.
Air-cooled heat exchangers eliminate the need for water
treatment and the need for disposal or recycling of solu-
tions of antifreeze.82 The Volkswagen “beetle” uses an air-
cooled engine. Texaco is marketing an “Extended Life
Anti-Freeze/Coolant” for cars and light trucks that lasts for
100,000 miles. Engine coolants can be recycled
profitably.83
IV. INHIBITION OF CORROSION
Despite man’s best efforts, many objects have their life-
times shortened by corrosion.84 The corrosion of metals is
an electrochemical process:
M D M n  n e
The forward reaction takes place at the anode, the reverse
at the cathode. An electrically conducting pathway is
needed to complete the circuit. Corrosion is often localized,
forming pits and crevices wherever the passivating layer of
oxide is broken by aggressive anions. Galvanic corrosion
can occur when two dissimilar metals are joined, one be-
coming the anode and the other the cathode. Magnesium
and zinc have been used as sacrificial anodes to protect
steel from rusting in pipelines, ships, hot water heaters, and
other equipment. A sprayed zinc anode has been used to
protect the steel bars in concrete highways from the effects
of deicing salts.85 Environmental effects such as the pH,
nature and concentration of anions, concentration of oxy-
gen, and temperature influence the corrosion process. Liv-
ing organisms, such as bacteria, sometimes produce
metabolites that cause corrosion.86 This is also true of
buildings and monuments made of stone, on which
biofilms can increase deposition of pollutants as well as
398
produce metabolic acids.87 Acid rain is particularly hard on
limestone, marble, and sandstone, which is held together
by carbonates. Genetically engineered aerobic bacteria
form a protective film on surfaces in cooling water systems
that cuts corrosion of steel, stainless steel, copper, and
brass by 35- to 40-fold, by thwarting the growth of the
usual corrosion-causing bacteria.88 This could be cheaper
and less damaging to the environment than treatment with
biocides.
The recovery of artifacts from the sunken ship, Titanic,
shows the results of corrosion over 89 years at 0°C and pH
8.2 under 2.5 miles of water.89 Aided by bacteria and other
agents, steel had corroded to give FeO(OH), Fe2O3, and
FeCO3. Lead carbonate and lead sulfide were derived from
the paint. Brass had corroded to Cu(OH)Cl. There was a
slow conversion of silver to silver chloride.
Where possible, materials that will not corrode should be
chosen.90 These include glass, plastics,91 and ceramics.92
The first and last are brittle so that when they are used in the
chemical process industry, it is usually as a lining for a steel
vessel. New ceramic composites consisting of silicon car-
bide or alumina matrices reinforced with nicalon ceramic
fibers have reduced brittleness and resist heat, erosion, and
chemicals. (See the earlier discussion for improved ceramic
fibers and less brittle ceramics.) Glass linings and piping
may be used more in the food and pharmaceutical indus-
tries, which require high purity with a minimum of contam-
ination. Plastics reinforced with glass or graphite fibers (i.e.,
composites) may achieve much wider use in the future for
noncorroding bridge decks, utility poles, and other exposed
surfaces. This would circumvent the problem of concrete
deteriorating under the influence of deicing salts. The use of
sand, instead of deicing salts, would also accomplish this.
The use of the more expensive calcium–magnesium ac-
etates in place of the sodium chloride might also do it with
less corrosion, contamination of water supplies with sodium
ion and death of vegetation along roads. The use of recycled
poly(ethylene terephthalate) to protect the reinforcing steel
rods in the concrete from corrosion has been demon-
strated.93 Polytetrafluoroethylene resists corrosion and
chemical attack well, but creeps, so that it, too, is restricted
to equipment linings.94
Titanium resists corrosion well, but is expensive.95 Tan-
talum is also expensive. Stainless steel and other nickel al-
loys are cheaper for use in equipment and resist reagents
such as formic acid.96 The commonly used Monel metal is
an alloy of 66.5% nickel and 31.5% copper. One of the best
steel alloys contains 20% chromium, 29% nickel, 2.5%
molybdenum, and 3.5% copper. Its rate of corrosion is 28
m/yr. Lasershot peening can be used to treat the surfaces
of metals to improve resistance to corrosion and extend the
lifetime up to five times.97
Chapter 13
A variety of reagents are used to inhibit corrosion.98 The
shift from solvent-based to water-based paints, cleaning so-
lutions, inks, cutting oils, and such, will require increased
use of such inhibitors. Corrosion can be inhibited in vari-
ous ways. A reagent may complex with the metal surface
and alter the redox potential of the metal or prevent ad-
sorption of aggressive ions. A passivating layer may be
formed and stabilized. The diffusion of oxygen to the sur-
face may be inhibited or the oxygen in the surrounding
medium may be scavenged. The surface may also be iso-
lated by application of a protective coating of another metal
or a polymer.
Chromate ion is an anodic inhibitor for steel that passi-
vates the surface. Because chromate is toxic, it is being
replaced99 with molybdates. Chromate works in the ab-
sence of oxygen. The replacements, molybdate and
tungstate, require oxygen to be effective. Alkylphospho-
nic acids perform as well as chromate and have superior
adhesion.100 Silanes, such as 1,2-ethylenebis(triethoxysi-
lane), are also being studied as replacements for chro-
mate.101 Corrosion-inhibiting pigments may contain
chromate or lead.102 Red lead, Pb3O4, was a popular pig-
ment in corrosion-inhibiting primers for steel. These are
being replaced by calcium and zinc molybdates or phos-
phomolybdates. Selective precipitation of calcium or
magnesium carbonates on cathodic areas or formation of
phosphate films restricts access of oxygen to the metal
surface. Hydrazine and sodium sulfite are used to scav-
enge the oxygen from boiler feedwater.
Organic inhibitors may adsorb on the whole surface. In
hydrophobic fatty amines, the amine coordinates with the
metal and the long carbon chains stick out from the surface.
Carboxymethylated fatty amines (i.e., N-substituted
glycines) chelate the metal on the surface. If a chelating
agent forms an insoluble surface coating, it may be a good
corrosion inhibitor. If it forms a soluble chelate, corrosion
may be enhanced. Alkylcatechols also inhibit corrosion of
steel. [Catechol forms strong chelates with Fe(III).] Benzo-
triazole protects copper from corrosion by formation of a
copper(I) chelate. Ethynylcyclohexanol adsorbs to steel,
then polymerizes (13.19).
Volatile corrosion inhibitors can be used with objects
stored in closed containers, such as tools during shipment.
A typical one is a dicyclohexylamine salt that dissociates to
produce the amine (13.20).
Low molecular weight copolymers of styrene with
maleic or acrylic acid have been used as their N,N-
dimethylethanolamine salts to prevent corrosion of zinc
and aluminum in coatings applied from water.103 Corro-
sion-resistant binders for magnetic tapes have been pre-
pared from diaminoquinones (13.21).104
Chemistry of Longer Wear
13.19
13.20
13.21
This diol was mixed with other diols, then reacted with
diisocyanates to form polyurethanes. The electrically con-
ducting polymers, polyaniline and polypyrrole, prevent
corrosion of steel.105 One of the best formulations uses
polyaniline with zinc nitrate, which is then covered with an
epoxy resin topcoat. Polyorganosiloxanes have been
grafted to starch using the sol–gel method with alkoxysi-
lanes. These materials have been complexed with cerium
ions to provide corrosion protection for aircraft that is ex-
pected to be 50% cheaper than conventional coatings.106
Chemical process plants often use epoxy, acrylic,
polyurethane, and other coatings to prevent corrosion.107
Food cans often have epoxy resin linings. A coating made
by the plasma polymerization of a 1:1 perfluorobutane–hy-
drogen mixture protected copper from aqueous corro-
sion.108 Auto makers often use electrogalvanized steel
399
sheet with a 4- to 14-m coating of zinc.109 Automobile
frames are given a phosphatizing treatment before painting
to help protect against road salts. This produces a surface of
Zn3(PO4)2, Zn2Fe(PO4)2, and Fe3(PO4)2. Zinc phosphate
has been used as a pigment in vinyl paints to replace zinc
chromate for the prevention of corrosion of steel.110
Phenylphosphonic acid has been used (without zinc) in sol-
vent-borne paints for in situ phosphatizing.111 Steel coated
by the polymerization of trimethylsilane in an argon–hy-
drogen plasma outperformed the current phosphated galva-
nized steel system.112 If this can be done for a whole auto-
mobile, it will reduce the problem of contamination of
wastewater with zinc and phosphate.
The hydroxyl groups on the surface of steel have been
treated with 3-aminopropyltrimethoxysilane to produce an
amine surface for reaction into an epoxy resin for corrosion
protection.113 The iron in a steel surface has been used as
part of a redox initiator for free radical polymerization of a
mixture of styrene and 4-carboxyphenylmaleimide at room
temperature to produce uniform pinhole-free films 1-m
thick.114 Terpolymers of maleic anhydride, styrene, and
C4–C18 alkyl acrylates have been used as corrosion in-
hibitors for aluminum flake pigments.115 (The anhydride
may react with hydroxyl groups on the surface.) The use of
lamellar mica in organic waterborne coatings for steel re-
tards corrosion by limiting ingress of water.116
Porcelain enamel is also used to protect steel. Kitchen
pots of this material were in common use before the
400
widespread adoption of aluminum and stainless steel pots.
The main problem with enameled steel is that the coatings
can chip on impact. Coatings of Portland cement are used to
cover steel pipes. The use of electroplating, flame spraying,
explosion cladding,117 hot-dipping, chemical vapor deposi-
tion, ion implantation, and others, to provide surfaces of
metals more resistant to corrosion was covered in Chap. 4.
Films of oxides can protect underlying metals. Magne-
sium and aluminum form surfaces that protect them in this
way. To prevent the formation of a dull powdery surface,
some aluminum surfaces, such as those for use on the exte-
riors of buildings, are anodized electrochemically in sulfu-
ric acid, which produces a shiny film of alumina containing
some sulfate and water. It is no longer necessary to use
chromate in anodizing.118 The anodized surface of alu-
minum can be protected by addition of chelating agents,
such as 8-hydroxyquinoline and benzotriazoles, in a seal-
ing coating of isostearic acid.
Cooling water treatment119 involves not only corrosion
control, but also prevention of deposition of scale in pipes.
Polyaspartic acid (prepared as in Chap. 12) can be used as
a dispersant and inhibitor of mineral scale.120 Magnetic
fields applied outside the pipes can reduce calcium carbon-
ate buildup or produce a softer less tenacious scale of arag-
onite instead of the usual crystal form, calcite.121 A pulsed
field can keep some of the crystals suspended instead of de-
positing. Magnetic fields also do this for carbon scale on
stainless steel equipment in oil refineries and for sodium
fluorosilicate scale in the manufacturing of phosphoric
acid. This should be simpler and cheaper than adding a
chemical to do the job.
V. MENDING
Mending and patching can make many items last longer so
that they do not need to be replaced as soon. The chemistry
may have to be different when this has to be done at room
temperature on something that was done at elevated tem-
perature in the factory. A scratch or chip in the baked-on fin-
ish on a car or an appliance may have to be touched up with
a different coating dissolved in a solvent. Epoxy body sol-
der for auto body repairs has to cure at room temperature.
The challenge, of course, is to make the repair as strong and
durable as the original material, and to do so even if the sur-
face preparation has been less than perfect. Plastic wood and
patching plaster are familiar to many persons.
The iron-on patch was a big step forward in repairing
clothing. The hot-melt adhesive used on it must adhere well
to the fabric initially and through repeated laundering or
dry cleaning, must not soften in the clothes drier, must not
be damaged by repeated flexing in use, and must be appli-
Chapter 13
cable with a home iron under conditions that may not be
well controlled. One material that is used is a terpolyamide
composed of 6, 6/36 and 6/12 nylons that softens at
100–150°C.122 (The numbers refer to the number of carbon
atoms in the ingredients with those in the diamine being
given first.) Such hot-melt adhesives are also available as
fusible webs that can be used to reinforce fabrics.123 Al-
though these adhesives are not altered chemically when
they are applied, it should be possible to develop some that
will cure to tougher polymers on application. A mixture of
microencapsulated diepoxide and curing agent would cure
when the capsules were ruptured by heat or pressure. Some
adhesives, such as that sold for installing Velcro fasteners,
cure by evaporation of solvent. Velcro fasteners on sticky-
back tape (that contains no solvent) are now available com-
mercially. “Shoe Goo II” applied to worn spots on shoes
can extend the life of the shoes appreciably. It appears to be
a thick solution of a rubber in a mixture of propyl acetate
and petroleum distillate. Similar solutions of polymers are
available for mending broken china, and other items. Ad-
hesive tapes on release paper can be removed and used to
hem garments (i.e., to replace sewing). Glue sticks are also
available for trimming, and putting in hems, zippers, and
what not. Some of these techniques should be applicable to
putting replacement liners in pants pockets.
The weak links in clothing include knees, elbows, pock-
ets, and zippers. Ideally, these should be made more durable
in the first place. Zippers with plastic (properly stabilized)
teeth large enough not to catch on the adjacent fabric, on a
strong fabric backing, should not wear out before the rest of
the garment. Stronger and thicker, if necessary, cloth could
be used for the pockets. Areas of wear, such as knees, el-
bows, and seats could be reinforced with strong fabric.
When the sharp points of shirt collars are badly worn, the
collars can be removed and the shirts worn without them.
Clothing that wears out beyond the ability to patch it can
sometimes be used for other purposes.124 Long pants with
worn-out knees can be converted to shorts. A long-sleeved
sweater with worn-out elbows can be converted to a short-
sleeved one. A dress can be cut off to a blouse. Worn-out
sweaters can be converted to mittens. Portions of one worn
out garment that are still good can be used to patch another.
Sections of adult clothing that are still good can be con-
verted to clothing for children. In earlier years, the scraps of
clothing went into patchwork quilts or braided rugs. Old
rags are also useful for cleaning around the house.
VI. MISCELLANEOUS
The biocides needed to protect wood and many other items
were covered in Chap. 3. Flame retardants125 are used
Chemistry of Longer Wear
sometimes in fabrics and in plastics. In one sense, they may
be thought of as compounds that make objects last longer.
Typically, they are compounds that contain high levels of
chlorine, bromine, or phosphorus. Antimony oxide is often
used with the halogen compounds as a synergist. Hydrated
aluminum hydroxide is also in common use. To be effec-
tive, these materials have to be used at such high levels, of-
ten 10–40%, that the physical properties of the polymer are
lowered appreciably. The nanocomposites of clays in poly-
mers mentioned earlier burn less readily than the unfilled
polymers, without losing strength from the filler. The use
of the halogen compounds conflicts with efforts to reduce
their use, as discussed in Chap. 3.
The use of polymers that are inherently resistant to igni-
tion seems preferable to trying to protect polymers, such as
polyolefins, that are much more flammable. Aromatic
polyamides and phenol–formaldehyde resins resist ignition
and tend to char in a flame. They have been used in fire
suits. Efforts should be made to minimize possible sources
of ignition. This includes removal of smoking materials,
charcoal lighter fluid, candles, paint thinner, kerosene
heaters, or others, from the household. An electric stove is
less likely to ignite clothing than a gas stove. A screen in
front of the fireplace also helps. Smoke detectors and auto-
matic sprinkler systems also help and are required by law
in many localities.
VII. THE FUTURE
Chemistry can provide stronger, more durable materials
that will last longer. Studies of the ways that polymers and
other materials degrade and wear out may lead to new ways
to intercept the processes. This may mean the design of
new stabilizer systems, new methods of construction or
new polymers.
The problem of overconsumption by the materials-ori-
ented societies of industrialized nations is a difficult one that
must be solved for a sustainable future.126 A possible ap-
proach is to make the real cost of an item apparent to the pur-
chaser at the time of purchase. This might encourage the
purchaser to buy the item based on the lowest cost per unit
of performance instead of the lowest initial cost. The label
might contain items such as the cost of the container, cost of
the product, cost for each use, expected lifetime, cost per
month or year, amount of use to be expected before resharp-
ening is needed, and more. This would show that the cost of
an item packaged in a throwaway container is higher than
that of one packaged in a reusable container. A customer
would have a choice of paying 10 cents for a throwaway
glass bottle or 1 cent per use for a refillable glass bottle. A
saw of poor steel that had to be sharpened every few months
would be less desirable than one of good steel that lasted 10
401
years before resharpening was needed. A label-rating sys-
tem might also be used. This might be a list of features of
good construction with those in the item for purchase being
checked. The presence of dovetailed joints on drawers in
furniture or double-sewn seams on clothing are examples.
There are examples of such required rating systems in
use today, at least in the United States. New cars are re-
quired to have the expected miles per gallon of fuel posted
on them. Electrical appliances, such as hot water heaters,
are required to have energy-efficiency ratings on them.
Foods in the grocery store must be labeled with the price
per unit weight as well as the price of the package. The
source of the ratings might have to be a government
agency, such as the U. S. National Institute of Standards
and Technology. Private testing laboratories are also suit-
able, as long as their ratings are thorough and objective.
Underwriters Laboratories does this for electrical equip-
ment. Consumers’ Union does it for many consumer goods.
Materials scientists may have to help in devising additional
accelerated tests, if none exist today. Frequently, the stan-
dard methods already certified by the American Society for
Testing and Materials will suffice.
The jobs that will be lost in the manufacture of throw-
away items will be counterbalanced by an increased num-
ber of jobs in maintenance and repair. Many items are dis-
carded today because it is cheaper to buy a new one than to
repair the old one. This calls for research on new automated
methods of repair as well as on new designs that make re-
pair simple. Increasing the cost of disposal may also help.
(See Chap. 17 for more on environmental economics and
Chap. 18 for greening of consumers.)
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RECOMMENDED READING
1. D. Klamann, Ullmann’s Encyclopedia of Industrial Chem-
istry, 5th ed., 1990, A15, 505–506 [recycling oil].
2. M.P. Stevens, J. Chem. Ed., 1993, 70, 445, 535, 713 [addi-
tives and stabilizers for polymers].
3. R. Dagani, Chem. Eng. News, Dec. 15, 1997, 11 [three-laser
method for making diamond coatings].
4. Y. Waku, N. Nakagawa, T. Wakamoto, H. Ohtsubo, K.
Shimizu and Y. Kohtoku, Nature, 1997, 389, 49 [ductile
ceramic].
EXERCISES
1. Make a list of weak links in products that you use.
How might these be replaced to make products that
would last longer?
2. List some things that you have found difficult to re-
pair. How would you redesign them to make them
easy to repair?
3. Do you have anything in your house that has been
made from scraps that might have otherwise been
thrown out?
4. Visit a fabric store to see what chemistry is there.
5. Devise a method to protect buildings of sandstone,
limestone, and marble from acid rain.
6. What items of plastic in your home have worn out
recently? Have there been any premature failures?
What could be done to make such products more
durable?
7. Deicing salts can cause concrete to deteriorate.
What could be put in or on the concrete to prevent
this? How might one polymerize a monomer in the
concrete to make it stronger and more durable?
8. The pink polyvinyl chloride strapping on the beach
chairs developed brown splotches in one season,
despite periodic treatment with a liquid supplied by
the supplier. Diagnose the problem and suggest a
solution.
14
Chemistry of Recycling
I. WASTE
The minimization of waste by the chemical industry was
discussed in Chap. 1. The waste to be discussed here is mu-
nicipal solid waste. This is the trash discarded from homes,
businesses, construction sites, schools, or others. For a sus-
tainable future, it will be necessary to recycle as much of
this as possible. The amount of waste varies with the coun-
try (Table 14.1), with the United States leading the list as
the world’s foremost throw-away nation.1
The quality of life does not follow this order. Several of
the countries have higher incomes per capita and life ex-
pectancies than the United States. Several of the countries
that compete with the United States in trade discard less
waste per person. The overconsumption that leads to so
much waste has implications beyond the boundaries of the
country in question. For example, the United States obtains
chromium and platinum from South Africa, calcium fluo-
ride from Greenland, and tungsten from China. The devel-
oped nations import beef, woods, bananas, cocoa, coffee,
pineapples, shrimp, and other consumables, from tropical
countries. The developed nations are partly responsible for
any environmental degradation involved in the production
of these crops.
The United States generated 208 million tons of munic-
ipal solid waste in 1995.2 This amounts to 4.3 lb/person per
day. It consisted of 37.6% paper and paperboard, 15.9%
yard trimmings, 9.3% plastics, 8.3% metals, 6.6% food,
6.6% glass, 6.6% wood, and 9.0% of other materials by
weight. Containers and packaging accounted for 34.1% of
the total. (In 1996, 209 million tons of municipal solid
waste was generated, together with 136 million tons of con-
struction and demolition waste.3) A study in Clark County,
Washington, showed that 2.5% of the material discarded
was reusable as it was.4 The reusable items included food
407
in the original containers, furniture, cosmetics; nuts, bolts,
appliances, toys, clothing, carpet, wood building materials
(41% of the total), plastic buckets, and ornamental glass.
The average business employee in the United States throws
away 250 lb. of paper per year.5 The advent of computers
and photocopiers has not reduced the amount of paper used
in offices.6
Only 27% of the municipal solid waste generated in the
United States in 1995 was recycled. (More than 7000 curb
side recycling programs and more than 9000 drop-off cen-
ters were in operation in 1995. The latter are energy-inten-
sive, because people usually drive to them in their cars.)
The recycled material included 40% of the paper and pa-
perboard, 38% of containers and packaging, 52% of alu-
minum packaging, 54% of steel packaging, 52% of paper
and paperboard packaging, 27% of glass packaging, 14%
of wood packaging, and 10% of plastic containers and
packaging.2 Office paper was recycled at the rate of 44%,
magazines at 28%, clothing at 16%, tires at 17%, nonfer-
rous metals at 70% (largely owing to recovery of lead bat-
teries), and ferrous metals at 31%. (By 1997, the recycling
rate for paper and paperboard had grown to 45%.7) The
United States exports 10 million tons of scrap iron each
year.8 It also exports a million containers of used clothing
to developing nations each year.)
The drop-off centers for voluntary recycling in
Delaware collect only 3.5% of residential waste in the
state.9 Industrial and commercial recyling raises the aver-
age for the state to 15.3%, the lowest among the northeast-
ern states in the United States. The highest recycling rate
among these states, 54.6%, is in New Jersey, where curb-
side collection of recyclables is mandatory. Communities
that have over 50% recovery of recyclables, such as San
Jose, California; Seattle, Washington; and Portland, Ore-
gon, have either mandatory programs or pay-as-you-throw
408
Table 14.1 Amount of Waste Generated by Various Countries
Country Waste per person per yr (tons)
United Sates 0.88
Australia 0.74
Canada 0.50
Denmark 0.40
Japan 0.35
Germany 0.34
Switzerland 0.32
Sweden 0.28
France 0.26
United Kingdom 0.25
Italy 0.24
Spain 0.22
systems (where the cost of waste disposal to the resident is
per volume or weight).10 (Minnesota has 1843 communi-
ties with pay-as-you-throw systems.11) Recycling has been
successful for apartments and condominiums as well as for
individual homes.12 For high-rise buildings, one system
uses a chute that goes to a turntable and compactor.13 A
person punches in the type of material on the floor control
panel and drops the material in the slot.
A model study on Long Island, New York, a few years
ago, demonstrated that it was possible to recycle 84% of
municipal solid waste. It is instructive to look at what some
industries have done to approach zero waste.14 Mad River
Brewing Co. in Blue Lakes, California, has a 97% recy-
cling rate. In addition to recycling the standard commodi-
ties, such as cans and bottles, paper is printed on both sides,
office paper is shredded for packing material, spent grain is
sold to local composting companies and farmers, employ-
ees repair and use wooden pallets, and wood scraps become
firewood. The Chrysler auto assembly plant in Newark,
Delaware, recycled 95% of waste plastic and cardboard,
85% of office paper, 100% of scrap metal, and 20% of
wooden pallets.15 In 1 year, this avoided disposal costs of
349,760 dollars for hauling and disposal at a landfill and
earned 212,288 dollars when sold. It should be possible to
reuse more of the wooden pallets, or to replace them with
more durable, reusable plastic pallets.
Landfills received 57% of the waste, and another 16%
was burned, usually with recovery of energy. Both of these
methods must be used carefully to prevent environmental
contamination. Landfills must be lined with liners that will
not be punctured by the heavy equipment running over
them, must have provisions for leachate treatment, and
monitoring wells to be sure that groundwater does not be-
come contaminated. The methane from them must be used
for fuel or vented to the atmosphere properly to avoid fires
Chapter 14
and explosions. Many Superfund sites are old landfills at
which these precautions were not taken. Several old land-
fills that replaced valuable wetlands can be seen from the
train as one passes through New York City. The Fresh Kills
landfill, the largest in the United States, is in a former
marsh on Staten Island in New York City. It is scheduled to
be closed at the end of 2001. Incinerators16 also have their
limitations. The emissions must be scrubbed to remove hy-
drogen chloride (from polyvinyl chloride and other chlori-
nated materials), nitrogen oxides generated during com-
bustion, mercury, dioxins, particulates, and such. The
remaining ash may contain toxic, heavy metal compounds.
Although incineration can recover some of the energy in
waste, it does not recover nearly as much as would be saved
if reusable items were used instead of throwaway ones. For
example, using and discarding 1000 plastic teaspoons con-
sumes ten times more energy than it takes to make one
stainless steel teaspoon and wash it 1000 times. 17 The
tragedy is that both of these disposal methods throw away
useful, valuable materials. Replacement of these puts addi-
tional pressure on the natural resource base.
II. RECYCLING
A. Introduction
Recycling18 is simplified if the material is free of contami-
nants. This requires as much separation as possible at the
source. The process is complicated because many con-
sumer items are made of more than one material. A steel
beverage can may have an aluminum top. The aseptic drink
box consists of several layers. Polypropylene film for foods
is usually coated with a barrier of polyvinylidene chloride.
It must be remembered that the paper, steel, aluminum,
glass, plastic, and such that need to be recycled come in
many different grades and compositions. These have been
optimized for specific uses, and they may not do well in
others. Thus, recycle may have to be to a less-demanding
use. Paper can be made by heating and grinding (thermo-
mechanical pulp) or by treating the wood with chemicals to
remove the lignin.19 It may or may not be bleached. Vari-
ous fillers, sizes, wet strength resins, and other additives
may be used on it. Some paper may be dyed or waxed.
Steel, aluminum, copper, and other metals are available in
many different alloys. Plain steel and stainless steel would
not be recycled together. Many different alloys are used in
stainless steel. A different alloy is used in the lid (e.g.,
0.35% Mn and 4.5% Mg) of the aluminum can than that in
the body (e.g., 1.1% Mn and 11% Mg) of the can.20 Deep
drawing is important for the body and ease of working the
pull tab is important in the lid. Aluminum pans are made of
Chemistry of Recycling
other alloys. Some scrap dealers will not even take the alu-
minum pans. (Aluminum is also alloyed for various uses
with iron, copper, silicon, lithium, chromium, lead, zinc,
and zirconium.) Window glass has a different composition
than that in containers and must be kept separate. Pyrex
glass has yet another composition.
The composition of plastics can vary even more. Vari-
ous polyethylenes vary in molecular weight, molecular
weight distribution, degree of branching, length of branch-
ing, crystallinity and so on. For polypropylene, variables of
tacticity and crystallinity must be included. Copolymers
can be random, block, or graft, and may sometimes contain
some of the homopolymers. The additive packages used in
the various polymers may vary. These include stabilizers,
impact modifiers, flame retardants, and dyes, among others
(as described in Chap. 13). Coatings and laminates can
cause additional problems. Clothing often consists of mix-
tures of fibers, as in cotton–polyester fabrics. Automobile
tires may have one rubber in the tread, another in the car-
cass, and a polyisobutylene liner inside as a gas barrier. In
addition, the degree of cross-linking in rubbers and other
polymers may vary.
Some curb side-recycling programs allow the comin-
gling of recyclable materials that are relatively easy to sep-
arate to save work on the part of the consumer. For exam-
ple, steel cans can be separated from aluminum cans with a
magnet. Separation of a mixture of containers is more dif-
ficult, but can be done. If the containers can be passed
down a line one at a time, on-line, then sensed by infrared,
visible, or ultraviolet light; by x-ray; or other rapid means,
blasts of air can remove them into the proper bins. Separa-
tion of mixed municipal solid waste, as done in Delaware
in past years, has been difficult.390 Aluminum separated by
eddy currents created in the metal includes both beverage
cans and pie tins, which are different alloys and do not re-
cycle well together. The glass recovered has a mixture of
colors of much less value than glass of separate colors. The
presence of ceramics in the glass interferes with its recy-
cling. Air classification can remove light objects such as
paper and plastic film. The plastic film interferes with the
repulping of the paper. A film of polyethylene terephtha-
late will come out in a different place than a bottle of the
same material. Sink-float techniques can also be used on
mixtures after removal of the paper and plastic films. This
may require shredding of metal and plastic containers, as
well as breaking the glass, so that containers with air inside
do not float. Compost made from the organic content of the
waste is contaminated with slivers of glass, as well as with
any toxic heavy metals that may be present in the pigments
on the paper.
The recycling techniques applied to the various clean
streams of materials will now be covered.
409
B. Paper
1. Recycling Versus Incineration
The recycling of paper21 has advantages over incineration
to recover energy from it,22 despite claims to the contrary
by some authors.23 Recycling saves more energy than that
obtained by incineration, because making new paper re-
quires energy to harvest trees, and so on. Recycling creates
three times as many jobs as incineration. In England, at
least, recycling helps the balance of payments and avoids
landfill costs. Those who advocate burning, rather than re-
cycling assume that fossil fuels will be used to harvest and
pulp the trees. Fossil energy may be used, but it does not
have to be in the future. People who recycle paper are
working toward a goal of 100% recycled fiber content, with
zero wastewater discharge from the plant. In a few in-
stances, this is possible today. As the techniques of recy-
cling gradually improve, the postconsumer content of recy-
cled paper is climbing.
2. Deinking
Some paper can be recycled without deinking. The result-
ing sheet will be somewhat gray, but can still be reprinted in
a legible fashion. For some uses, such as toilet tissue, there
should be no need for deinking or bleaching. Some recycled
fiber that has not been deinked can be added with a surfac-
tant in the making of new newsprint.24 Usually deinking is
required.25 Not all uses require the same level of deinking.
Sorted office paper can be converted to tissue, white liner
board, and other grades (containing 100% recycled fiber),
with less stringent optical requirements than printing and
writing grades.26 The paper is usually repulped in the pres-
ence of a base, a surfactant, and other additives at 45–60°C
for 4–60 min. A typical run may contain 0.8–1.5% sodium
hydroxide, 1–3% sodium silicate, 0.25–1.5% surfactant,
0.5–2.0% hydrogen peroxide, and 0.15–0.4% diethylenetri-
aminepentaacetic acid. The fiber is swollen by the sodium
hydroxide at pH 8–10, reducing the adhesion of the ink
to the fibers. The sodium silicate prevents the redeposition
of the ink, and the hydrogen peroxide counteracts yellow-
ing. The diethylenetriaminepentaacetic acid ties up any
metal ions present that might cause the hydrogen
peroxide to decompose. The ink27 particles are then re-
moved by washing the pulp or by flotation. Washing is best
for small particles of ink (2–20 m) and flotation
for larger particles (40–250 m). The presence of clay filler
particles from magazines improves the efficiency
of flotation deinking, so that newspapers and magazines
are often repulped together.28 Pressurized flotation cells are
better than those operating at atmospheric pressure.29 Col-
umn flotation is superior to that done in a tank.30
410
In some flotation deinking, calcium chloride is used
with a long-chain fatty acid to make the ink particles
hydrophobic.31
Mechanical means are also used to enhance the removal
of the ink from the fibers. Passing the fibers between rotat-
ing disks can help.32 When ultrasound is used, there is less
need for chemicals, and the resultant pulp is stronger.33
Steam explosion, during which paper containing 50%
moisture is passed through a hot coaxial feeder, reduces the
need for chemicals and eliminates the need for flotation.34
This process can also handle laser and xerographic inks,
which can be difficult to remove by other means. There is
some loss in tensile strength.
The removal of toners (the inks) used in photocopiers
can offer problems.35 Toners are low-melting resins (e.g.,
styrene-1,3-butadiene copolymers, acrylic polymers, or
polyesters), containing carbon black.36 Various techniques
are used to facilitate their removal. One way is to melt them
during the deinking process so that they agglomerate, then
to cool the mixture to harden them, and then to remove
them by screens.37 Another is to pass the paper slurry
through a twin-shaft kneader at room temperature, which
shifts the particle size to one which flotation can be used to
remove them.38 Ultrasound can be used to break up toner
particles for easier removal.39 1-Octadecanol enhances de-
tachment of toners and increases flotation efficiency.40
Planetary mixing starting at 90°C and ending at 25°C can
help.41 Cationic surfactants, such as cetyltrimethylammo-
nium bromide, can act as both the frothing agent and col-
lector in the flotation deinking of photocopier paper.42 Ri-
coh has devised a way to remove the toners from sheets of
copy paper by treating with a hot solution, then drying.43
Toshiba has devised toners that can be decolorized by heat
or solvent.44 Photoerasable toners have been made based
on copolymers of methacrylophenone.45 It should also be
possible to base them on dyes that bleach in ultraviolet
light. Electrophoretic inks, in which a pigment in a micro-
capsule responds to an electric field, may also be useful in
reusable paper.46 Thus, the sheet of paper can be used again
in the same office without repulping.
3. Stickies
Paper may contain a variety of other materials that must be
removed during repulping.47 These include sizing agents,
retention aids, wet and dry strength additives, coatings,
fillers, and others. In addition, recycled paper may contain
staples, paper clips, pressure-sensitive adhesives (as on U.
S. stamps and return address labels), hot melt adhesive (as
in book bindings), wax, plastic tapes, polystyrene windows
in envelopes, and so on.48 Pressure-sensitive adhesives
may contain various rubbers, such as styrene-1,3-butadiene
copolymers, polyisoprene, natural rubber, and poly(1,3-bu-
Chapter 14
tadiene), plus tackifying resins, such as esters of rosin. Hot-
melt adhesives49 may contain polyethylene, copolymers of
ethylene and vinyl alcohol, wax, and such. Coating binders
may be styrene-1,3-butadiene copolymer rubber, polyvinyl
acetate, polyvinyl chloride, vinyl acrylates, or others. Bar-
rier films may be made of wax, polyethylene, polypropy-
lene, polyethylene terephthalate, or nitrocellulose. Radia-
tion-cured inks may be based on epoxyacrylates, polyol
acrylates, urethane acrylates, polyester acrylates, and other
such. Although some of these materials can be removed by
screens, others tend to plug screens, and they may form
spots in the recycled paper.50 Collectively, they are referred
to as stickies. One way to remove them is by treatment with
supercritical (sc) carbon dioxide, containing a lower
alkane, such as pentane.51
Air Products has devised a process using oxygen,
sodium hydroxide, sodium silicate, and the like, at
180–200°C at 60 psig, followed by treatment with a reduc-
ing agent, such as sodium hydrosulfite, that removes dyes,
inks, wet-strength resins, and detackifies adhesives in
mixed office wastepaper.52 Another system uses 1% min-
eral spirits, 1.22% sodium silicate, and 3% sodium hydrox-
ide in water at 50°C.53 The polymers present become scav-
engers for the ink, forming particles that can be removed by
screening. In more common processes, the stickies that
cannot be removed by screening are detackified, agglomer-
ated, or dispersed.54 Talc is sometimes added to reduce
tackiness. Dispersants, such as fatty alcohol ethoxylates
and naphthalene sulfonates, can keep some of them in a
colloidal state in which they will not interfere. Ultrasound
can help in dispersing them.55 Flocculation with high
molecular weight cationic polymers can also be used. The
method used will depend on the nature of the stickies and
the equipment in the mill. Some pressure-sensitive adhe-
sives become more spherical on heating, so that they can be
removed by centrifugation or screening techniques.56 Most
hot-melt adhesives come out on screens as strips and frag-
ments.57
Some work has been done to redesign the materials so
that the stickies problems do not occur. Waxes used on
3–5% of corrugated cardboard cartons (for food items)
complicate recycling,58 although there is one system that is
said to be able to reduce the wax from 30 to less than 1%
mechanically.59 Waxes made with a low percentage of
stearic acid and a few tenths of a percent of a fatty alcohol
ethoxylate redisperse during alkaline repulping.60 Paper
coated with a combination of zein (from maize) and paraf-
fin wax can be dewaxed with the enzyme, -chy-
motrypsin.61 Acrylic polymers, which may contain car-
boxylic acid groups, can be used to replace wax on
corrugated boards.62 Polycaprolactone–paper composites
have good water resistance and biodegradability.63 These
Chemistry of Recycling 411

14.1

might be able to replace objects made of waxed paper. The The deinked pulp can be made into fine writing and print-
conditions of alkaline repulping would have to be such that ing papers. Old newspapers have been converted to super-
the polyester was hydrolyzed. soft tissue using enzymatic repulping.71 Enzymes should
Repulpable hot-melt adhesives can be made with soft- be useful in removing soy-based inks.
ening points high enough that they will not soften during
repulping, or they can be made dispersible in aqueous 5. Changes in Fibers in Reuse
base.64 Binders for deinkable inks have been made by the
Recycled paper contains more fines and shorter fibers.
reaction of phthalic anhydride and neopentyl glycol (2,2-
Some strength is lost in repeated cycling of thermome-
dimethyl-1,3-propanediol), or trimethylolpropane to form,
chanical fibers (as in newspapers).72 The surface becomes
polyesters.65 Dyes that can be bleached by reduction during
rougher and the ratio of oxygen to carbon goes up, perhaps
repulping may offer advantages.66 The use of dyed paper
by oxidation. There is a substantial change in the fiber
could also be reduced. Most stickies are polymers. Substi-
properties in the first cycle, but most physical properties
tuting copolymers made with acrylic acid, methacrylic
stabilize after about four cycles.73 This is thought to be due
acid, or maleic anhydride would make them soluble in the
to a drop in interfiber bonding and not to loss of strength of
repulping medium.391 Such polymers are widely used in
the individual fibers.74 There is an irreversible hornifica-
water-based coatings and adhesives (see Chap. 8). Another
tion of some mechanical pulps on drying that reduces fiber
possibility is to use polyesters from the polyglycol diacids
bonding.75 Beating (i.e., mechanical action to produce
(14.1) sold by Hoechst Celanese.67 These could be made to
more fibrils on the surfaces of the fibers) can restore the
be soluble in water.
strength properties lost on drying and rewetting.76 The
The problem of the polystyrene windows in envelopes
minimum mechanical force necessary to obtain the desired
could be solved by reverting to the use of glassine paper
result should be used throughout the repulping process.
windows. Glassine paper is made by a combination of heat
This may mean that some of the action of the machines
and pressure. Its cost might be reduced if it could be made
used with virgin pulp may need to be made gentler.
directly in the paper to be folded into the envelope by pres-
In one study, newspaper was recycled without the use of
sure and microwave heating. Ultrasound might help in the
water.77 The paper was fiberized mechanically, and the
process. Windows that are just cutouts are now in use and
fibers were air-laid to produce a new sheet. It was neces-
seem to function satisfactorily. The U. S. Postal Service is
sary to treat the fibers first with ozone, then with ammonia
to change the pressure-sensitive adhesive on stamps to one
to achieve good interfiber bonding when the air-laid sheet
that will repulp more easily. Going back to the water-moist-
was pressed. The tensile strength of the resulting paper ap-
enable ones used until recently would solve the problem.
proached that of the original newsprint. Such a process
would eliminate aqueous effluents.
4. Enzymatic Repulping
6. Extent of Recycling of Paper
No deinking chemicals are necessary when old newspapers
are repulped with a cellulase.68 The larger uninked fibers By using the techniques outlined in the foregoing for aque-
are retained by a plastic mesh screen, whereas the smaller ous repulping, some mills have been able to obtain very
inked ones go through to a separate vessel. Enzymes facil- high rates of recycle of postconsumer paper. U. K. Paper
itate toner removal, increase brightness, improve pulp uses deinked pulp of 75–100% recycled content.78 Bridge-
drainage, preserve fiber integrity, and lower chemical costs water Paper, in England, produces newsprint that averages
in the repulping of mixed office wastepaper.69 The 95% recycled content.79 Some urban minimills80 can make
drainage is best when the enzyme is combined with a poly- recycled linerboard from 100% old corrugated contain-
acrylamide containing quaternary ammonium groups. 70 ers.81 A mill next to the Fresh Kills landfill on Staten Is-
412
land, New York, makes 100% recycled containerboard.82 It
“harvests an urban forest.” New Jersey had 13 paper mills
running only on wastepaper and 8 steel minimills using
scrap steel in 1999. The total annual output of these two in-
dustries was more than 1 billion dollars.83 Some of these
minimills are able to operate closed systems with no efflu-
ent.84 Zero liquid effluent is now practical for corrugating
medium and linerboard mills.85 A few other mills have
achieved it.86 A Kimberly–Clark mill in Australia will pulp
thinnings from Pinus radiata plantations with magnesium
bisulfite, bleach with hydrogen peroxide, recover all spent
sulfite liquor, capture all gases from cooking and either
compost all fines or use them for fuel.87 Further study of
the use of reverse osmosis, ultrafiltration, biological oxida-
tion, and such, may make it possible for other mills to have
zero effluents. Paper mill effluents have been notorious for
their contamination of streams.88 Even the natural resin and
fatty acids in the wood can be toxic to fish.89 It would be
better to recover these acids for industrial use, as is done in
many mills.
7. Nonpaper Uses for Wastepaper
Mixed wastepaper can also be used for uses other than pa-
per.90 Extensive cleaning may not be needed in something
such as a wood-based composite that will be painted or
overlaid. Various composites have been made. These in-
clude (a) molding of paper fibers mixed with polyethylene
or polypropylene to form door panels, trunk liners for cars,
and plastic lumber; (b) nonwoven mats of up to 90% paper
fibers held together by synthetic fibers by entanglement or
thermal bonding; (c) wet-laid boards made with binders,
such as resins, asphalt, and such, for use as acoustical insu-
lating board; (d) composites of wood, paper fiber, and gyp-
sum or Portland cement, and (e) structural paper products
made from wet-formed waffle-like sections. A board from
50:50 wood cement is easy to saw and nail. Such a board
might be made from the calcium sulfate, derived from flue
gas desulfurization, and sludge from the recycling of paper.
It could replace present drywall. Putting two waffle-like
sections of re-formed, recycled paper together with an ad-
hesive produces a sandwich that is 30–200% stronger than
conventional corrugated fiberboard. Polypropylene, con-
taining 50% waste newspaper flour, is sold in Japan.91
Maleated polypropylene can be used as a compatibilizer.
Old telephone books and plastic milk jugs have been made
into flat panels and moldings normally made of wood in
Australia.92 They are twice as strong and three times as stiff
as wood. They repel water and are free of knots and defects.
Wastepaper shredded into 2- to 3-in. flakes is used in hy-
droseeding in Iowa.93 It breaks down into finer pieces in
the hydroseeder tank. Shredded wastepaper is used as ani-
Chapter 14
mal bedding instead of straw in Chester County, Pennsyl-
vania. It can also be used as packing around objects being
shipped in boxes in place of polystyrene “peanuts.” With
the proper flame retardant added, it can be used as insula-
tion in houses. Pencils can also be made of recycled
paper.94
8. Uses for Paper Mill Sludge
Many uses have been explored for paper mill sludge.95
(More than 4 billion kg are produced in the United States
each year.96) It can be used in making boards, tiles, plas-
tics; as animal litter; or even fed to cattle. One of the best
uses for the sludge from repulping mixed office wastepaper
is to mix it into newsprint to lower costs while producing a
higher quality pulp.97 Phenolic resin composites have been
made with paper sludge.98 Bacteria or fungi can convert pa-
per mill sludge to single cell protein. Yeasts can convert it
to ethanol. Methane can be produced from it by anaerobic
fermentation. Other disposal methods include composting,
land application, and incineration. (A record 200,000 tons
of nonrecyclable paper was converted to compost in the
United States in 1998.99) The best approach is to minimize
the amount of sludge formed by use of an acrylamide
copolymer as a retention aid to keep more of the fines in the
paper being made.100 The uses of sludges from the repulp-
ing of wastepaper will be limited somewhat by the pres-
ence of ink particles, fillers, and such. They should still be
suitable for many of the foregoing uses. The residue from
incineration of sludges might be used again as a filler for
paper. It has been made into glass aggregate used in roof-
ing shingles, asphalt, and sandblasting grit.101 Sludges
should be too valuable to dispose of in a landfill.
One proposal for the use of scrap wood not suited for the
making of paper is to raise termites on it.102 The methane
evolved would be collected and used. The termites would
be harvested for animal feed.
9. Nonwood Fibers for Paper
There is much concern about the loss of biodiversity as the
old-growth forests of the Pacific Northwest of the United
States and Canada are cut. Old-growth boreal forests sup-
ply 15% of the world’s paper pulp, and old-growth temper-
ate forests supply 1%.103 Efforts are being made to find
other sources for paper so that these forests can be pre-
served. In Canada, sawmill waste is the source of 60% of
the fiber for paper.104 This might also be used to make chip-
board for construction. Canada is the largest producer of
newsprint in the world.
Bags made from bamboo and sisal in Brazil were more
resistant to bursting than ones made from pulp from pine
trees.105 Paper can also be made from hemp, kenaf, wheat
Chemistry of Recycling
straw, rice straw, and bagasse (the residue left after the
juice is pressed out of sugarcane).106 If done properly, non-
wood can replace both softwood and hardwood pulps with
few problems and little loss in performance.107 Kenaf (Hi-
biscus cannabinus)108 and hemp can be grown in one sea-
son compared with a harvesting cycle of 15–25 years for
southern pine in the United States of America or 6–8 years
for Eucalyptus in Brazil.109 Hemp produces 3–6 tons/acre
per year, and kenaf 6–10 tons/acre per year, twice as much
as southern pine.110 Newsprint from kenaf is as strong as
that made from trees, is brighter, slower to yellow, and less
susceptible to ink run-off and smudging.111 However, its
price will not become competitive until larger amounts are
used. The chemical pulping of hemp, kenaf, and jute gives
high-quality pulp that costs too much for bulk applications.
Extrusion pulping with aqueous sodium hydroxide, sodium
sulfide, and such, has been used to make pulp that should
be competitive with wood pulp in a variety of paper appli-
cations.112 The quality is comparable with softwood chem-
ical pulp. Enzymatic pretreatment of the nonwoody plants
yielded paper, with as good or better physical properties as
conventional pulping, with much energy saved.113 Spain
saves wood by pulping wheat straw with 65% aqueous
methanol at 175°C for 75 min.114 Fibers pulped from
grasses, such as Phragmites communis (an invasive weed
in marshes of the eastern United States), with performic
acid were weaker, but could be used to replace 30–70% of
birch wood pulp.115 A mill to produce paper from flax
straw and maize stalks was set to open in Nebraska in
1997.116 It will produce currency paper, writing paper,
newsprint, and cardboard. Spent grain from a brewery has
been fractionated to produce a fraction containing 1–2%
protein, 30% cellulose, 60% hemicellulose, and several
percent silica that can be used in paper at a level of 10%.117
Greater production of paper from agricultural wastes will
decrease the pressure to cut forests. This might be encour-
aged by removing the subsidies and charging more for log-
ging in national forests in the United States. It might also
be encouraged by a tax deduction. Even more important is
to figure out how the consumption of paper can be reduced.
(The United States with 4.7% of the world’s population
uses 31% of the world’s paper and paper board.118)
C. Plastics
World consumers used 215 billion lb of the five most com-
monly used plastics in 1996.119 This included 41%
polyethylene, 23% polyvinyl chloride, 21% polypropy-
lene, 11% polystyrene, and 4% styrene–acrylonitrile
copolymers. The world production of polyethylene tereph-
thalate in 1996 was 9.8 billion lb. The United States’ plas-
tics use in 1995 was 71.2 billion lb, of which 27% was used
413
for packaging, 20% in building, 13% in consumer prod-
ucts, and the rest in a miscellany of uses. The use of plas-
tics continues to rise with each year. The consumption of
polyethylene terephthalate is growing at the rate of
15–20%/yr, with much of this going into bottles.
1. Recycling Problems
The recycling of plastics120 is not growing rapidly. In the
United States, less than 10% of plastics packaging is recy-
cled. Only 4% of plastic grocery bags is recycled (e.g., to
decking lumber).121 In 1993, only about 2% of all plastics
produced was recycled.122 Some recycling facilities are be-
ing sold to smaller companies by the large chemical com-
panies or are closing.123 One problem is obtaining an as-
sured stream of clean material to recycle. The few success
stories include polyethylene terephthalate, bottles, many of
which are returned under deposit legislation.124 In 1996
485,000 metric tons was collected in the world for recy-
cling. (Of this 330,000 metric tons was in North America.)
There is even a report of a shortage of these bottles for re-
cycling.125 These are used to produce foamed insulation,126
fibers for various applications, shower curtains, paint
brushes, and others. However, the recycling rate for
polyethylene terephthalate bottles dropped from 27.8% in
1996 to 25.4% in 1997, whereas total use was rising.127
During the same time period, the recycling rate for all plas-
tic containers dropped from 24.5 to 23.7%. Small amounts
of polyvinyl chloride in with the polyester can seriously
contaminate the batch.128
High-density polyethylene milk jugs are being recycled
into other containers, usually for nonfood uses, as well as
into drainage pipes, trash cans, grocery bags, traffic barrier
cones, and such. If they go into new food containers, they
must be in an inner layer in a laminate with virgin material
on the surface. The polypropylene cases of car batteries are
also recycled well. Although polyvinyl chloride can be re-
cycled into bottles, pipes, and window frames, it is recycled
less than other plastics.129
The plastics that are in other throwaway packaging130
are difficult to handle. They may be in thin films or con-
taminated with food residues, and may be in a great many
trash cans in a great many places. The high costs of col-
lecting and sorting raise the prices of recycled plastics to a
point that most manufacturers would rather use virgin plas-
tics. (The cost of the virgin resin does not include global
warming and natural resource depletion.) If the pieces of
plastic can be sent down a line one at a time, an on-line
spectroscopic analyzer can sort them. For example,
polyethylene and polypropylene can be separated by
pulsed laser photoacoustic technology.131 Hand-held de-
vices that work by Raman spectroscopy are also avail-
414
able.132 If the materials to be sorted are crumpled films,
laminates, core-sheath fibers,133 or polymer blends, such
systems will not work well. Foamed cups and “peanuts”
of polystyrene are voluminous and require some form of
densification to make transportation to the recyling center
economical.134
Many plastic objects are marked with a number inside
three chasing arrows: 1 is polyethylene terephthalate; 2
high-density polyethylene; 3 polyvinyl chloride; 4 low-
density polyethylene; 5 polypropylene; 6 polystyrene; and
7 other (including multilayer). Such a system allows a con-
sumer to place the used object in the proper bin, if such bins
are provided. The consumer must remember that the lid or
cap is often a different plastic from the rest of the container
and must be conscientious in looking for the numbers on
every piece. Curbside recycling is not going to provide that
many bins. Manual sorting at a recycling center might
work, but would be time-consuming. This means that some
automated system is required for the separation of the var-
ious plastics. Some companies that make plastics have
sought to encourage the recycling of their products by take-
back programs. duPont makes its spun-bonded polyethy-
lene mailing bags with 25% postconsumer high-density
polyethylene from milk and water jugs. The company col-
lects the used bags from its customers for recycling into
plastic lumber.135 As these mailing bags look very much
like their paper counterparts, they get into paper recycling
and cause problems as stickies.136 Waste polyethylene can
be used to hold together other waste materials to make new
products, as mentioned earlier under the recycling of paper.
Waste cedar fibers can be used with up to 60% waste
polyethylene to make plastic lumber.137
2. Recycling Methods
Recycling is easiest when only one polymer is present and
no separation is needed. Polypropylene fertilizer bags can
be reprocessed without additional stabilizers if they were
properly stabilized the first time.138 Because of the degra-
dation in aging and remolding, it is often necessary to add
additional stabilizers when a plastic is recycled into a new
plastic object.139 Carpets are often made with one poly-
mer in the facing and another in the backing.
Hoechst–Celanese has devised one made entirely from
polyester that should be easier to recycle at the end of its
useful life.140 This also simplifies what to do with scraps
from the manufacturing and installation processes. The
polyethylene terephthalate soda bottle is a mixture in that
it has a label and cap of polypropylene. Redesign has
eliminated the polyethylene base cup used formerly. It
may be possible to prepare an all-polyester soda bottle.141
The label might be replaced by ink jet printing. A shrink
Chapter 14
label of polyester is also possible, but care would be re-
quired in its installation because its softening point is
about 100°C higher than that of the current label of
polypropylene. A cap of polyester may also be possible if
crystallization of the polymer can be speeded up to
shorten molding cycles. Sodium bicarbonate and carbon-
ate have been used as nucleating agents to shorten the
molding cycles of recycled polyethylene terephthalate.142
(Bottle makers often add a crystallization inhibitor so that
the bottles remain clear. A cap would not have to be
clear.) The seal of the cap liner might have be made of a
different polymer, which in the small amount involved,
one hopes, would not interfere with recycling of the bot-
tles. duPont is marketing a glass fiber-reinforced molding
compound made from used soda bottles and x-ray film
from which the emulsion has been removed.143 The key to
this reuse is to prevent degradation of the molecular
weight by keeping the polyester dry to prevent hydrolysis,
minimizing oxidative degradation during recycle, and
keeping rogue materials, such as polyethylene and
polyvinyl chloride out of the system.144
Foamed polystyrene waste (15–35%) has been dis-
solved in a mixture of styrene and divinylbenzene for
copolymerization.145 This was followed by sulfonation to
produce an ion-exchange resin. High temperatures in an
oxidative environment tend to decrease the physical prop-
erties of recycled nylon 6,6.146 Polyvinyl chloride from
bottles, appliances, and pipes can be remolded into pipes,
with the addition of fresh stabilizer, with or without the ad-
dition of virgin polyvinyl chloride, without loss of tensile
strength or modulus.147 French auto makers are studying
ways of recycling polyvinyl chloride from cars at the end
of their useful lives.148 The material is used in seat covers,
dashboards, and trim. Greenpeace has accused the German
plastics industry of misleading the public on the amount of
polyvinyl chloride that is being recycled.149 According to
Greenpeace, 98% of polyvinyl chloride waste is dumped or
burned. An ingenious way has been found to remove the
paint from old car bumpers of polypropylene before recy-
cling.150 The bumper is cut into pieces, then run through a
series of four rolls at 100°C with the second roll running
slightly faster than the others. The polypropylene stretches,
but the paint does not so it flakes off.
3. The Use of Compatibilizers and the Handling of
Mixtures
Much effort is being expended on polymer blends to reduce
the need for separation and to improve the properties of the
recycled materials. Because most polymers are incompati-
ble with one another, this usually requires the addition of a
compatibilizer,151 or the preparation of one in situ. (Com-
Chemistry of Recycling
patibilizers are often block or graft copolymers, with parts
similar to each of the polymers that are to be made com-
patible.) A few examples will be given. A polypropylene
grafted with maleic anhydride has been used to compatibi-
lize blends of polypropylene and nylon 6,6.152 (The amino
end groups in the polyamide react with the anhydride
groups in the graft copolymer to form a new amide.) A
mixture of polyethylene terephthalate and linear low-den-
sity polyethylene can be compatibilized using 10% of the
sodium salt of poly(ethylene-co-methacrylic acid).153 Per-
haps, this could be used on a mixture of soda bottles and
milk jugs. Reactive extrusion of a mixture of polyvinyl
chloride and polyethylene with a peroxide and triallyliso-
cyanurate gave a compatible mixture.154 In this case, the
compatibilizer was formed in situ by grafting. The product
was a cross-linked copolymer. Moldings of a mixed waste
of polystyrene and polyethylene had increased strength.155
For this, the mixture was not compatible. The improvement
in properties was due to the separation of the less than 30%
polystyrene as fibers. Small amounts of hydrogenated
styrene–1,3-butadiene block copolymers have been used to
compatibilize mixtures of polystyrene and polyethylene.156
Blends of polypropylene and polystyrene have been com-
patibilized with 2.5% polystyrene-block–poly(ethylene-
co-propylene).157
Efforts are being made to handle mixtures typical of
waste streams. A mixture of polyethylene, polyethylene
terephthalate, and polyvinyl chloride bottles, typical of
those used in Italy, was molded with an elastomeric block
copolymer of styrene, ethylene, and 1,3-butadiene, to pro-
duce improvements in impact strength and elongation at
break.158 Solid-state, high-shear extrusion of mixed waste
linear low-density polyethylenes produced block and graft
copolymers in situ to achieve improved compatibility.159
For this, the free radicals were generated mechanically,
rather than through the addition of a peroxide. The result-
ing mixture was then remolded. The concept is expected to
be applicable to various mixtures of waste plastics, to elim-
inate the need for sorting them. This might be suitable for
the “gnarled fence posts” made from recycled materials
that are available at some garden stores.
A different approach taken by Rensselaer Polytechnic
14.2
415
Institute is to separate the polyolefin plastics in the domes-
tic waste stream.160 It is said to be able to reclaim 98% of
the plastics. The polystyrene is dissolved in mixed xylenes
at room temperature, low-density polyethylene at 75°C,
high-density polyethylene at 105°C, and polypropylene at
130°C. There may be problems with this scheme. Prior sep-
aration of polyvinyl chloride and polyethylene terephtha-
late may be required. Polypropylene film is often coated
with polyvinylidene chloride as a barrier coating. In addi-
tion, many polymers dissolve very slowly, even over days,
to give highly viscous solutions. (The higher the molecular
weights of the polymers, the greater these problems will
be.) After flash evaporation of the solvent, some of it will
remain in the polymer until the polymer is passed through
a vented extruder. Traces of solvent are difficult to remove
from viscous matrices.
4. The Use of Chemical Reactions in Recycling161
The concern about possible contamination of food contain-
ers means that they can be recycled to only nonfood contact
uses in the United States. To reuse polyethylene terephtha-
late in contact with food, it must be broken down, purified
(to remove metal compounds, colors, and such), and resyn-
thesized (14.2). This has been done by hydrolysis,
methanolysis, and glycolysis.162 (The solvolysis can be
complete in 4–10 min when microwaves are used with a
zinc acetate catalyst.163) (For nonfood uses, such as the use
of polyethylene terephthalate in magnetic tapes, it may be
sufficient to melt the polymer and filter out the chromium
or iron oxides.164)
The technique is also applicable to cross-linked
polyesters made from unsaturated polyesters and styrene,
as in the sheet-molding compounds used in cars and
boats.165 The ester linkages were broken by treatment with
ethanolic potassium hydroxide or by ethanolamine. The
latter was preferred, because no waste salts were formed by
neutralization, as they were with the potassium hydroxide.
The filler and glass fibers could be removed at this stage, if
desired. The alcohol-soluble product was suitable for use in
new bulk-molding compounds. A method that allows the
cross-linked polyester to recycled back into the same use
416
14.3
involves heating with propylene glycol, reesterification
with additional maleic anhydride and adding more
styrene.166 An alternative way to recycle the sheet-molding
compound would be to pulverize it and use it as a filler in
new sheet-molding compound. Waste polycarbonates can
be broken down by phenolysis.167 (Direct reuse by remold-
ing would be preferable when possible.) Polytetrahydrofu-
ran can be converted to monomer by a hot treatment with
hydrochloric acid on kaolin.168 The solid catalyst was still
active after repeated use.
Any condensation polymer containing ester, carbonate,
amide, imide, urethane, or similar groups can be treated in
this way to recover monomers or oligomers for making the
same or other polymers. Soluble products from cross-
linked polymers will usually have to be used in an applica-
tion other than the original one. Nylon 6 wastes from car-
pets, or other, have been hydrolyzed to the monomer
caprolactam (14.3).169 (The carpet backing left behind has
been tested as a filler in roofing shingles.) Phosphoric acid
can be used as a catalyst for the reaction.
Waste nylon carpet has also been pyrolyzed in a flu-
idized bed at 350°C over KOH/Al2O3 to recover 85% of the
caprolactam.170 Nylon 6 waste has been upgraded by reac-
tive extrusion with trimellitic anhydride (without solvent) to
produce polyamideimides, with number average molecular
weights of 9,000–30,000.171 Polyamides have also been
converted to monomers by treatment with ammonia.172
Polyurethanes can be degraded by aminolysis or transester-
ification to liquid products useful in adhesives, foams, and
composites173 (e.g., as hardeners for epoxy resins). General
Electric has devised a way to recover 4,4-hexafluoroiso-
propylidenebis(phthalic anhydride) from scrap polyimides
using lithium hydroxide in N-methylpyrrolidone at
225°C.174 The glass fiber, diamine, and bisanhydride are re-
14.4
Chapter 14
covered. The solvent and lithium hydroxide are recycled
back to the process. Waste phenolic resin has been liquified
in more than 95% yield by hydrogenolysis in hot tetralin
(the source of the hydrogen).175 The mixture of liquid phe-
nols (75% were cresols and xylenols) could be used to make
new phenolic resins. (When simple pyrolysis was used, the
yield of phenols was only 30–50%.176) This illustrates a
way to recycle a thermoset (i.e., cross-linked by heat) poly-
mer chemically, instead of just using it as a filler in a new
polymer. Supercritical water has been used to break down
polymers. Waste phenolic resin gave a mixture of phenols
in 28% yield.177 Polystyrene gave 92.4% selectivity for
styrene, 5.1% for toluene, and 2.4% for benzene.178 The dis-
tillation residue from the preparation of 2,4-toluenediiso-
cyanate allowed recovery of 80 mol% of the diisocyanate as
2,4-diaminotoluene.179
Oxidation of waste plastics, such as polyethylene,
polypropylene, polystyrene, poly(alkyl acrylates), and nylon
6,6, with NO/O2 for 16 h at 170°C, led to mixtures of car-
boxylic acids, for which uses would have to be developed if
this method was applied to large volumes of waste plastics.180
Hydrogenation of polyethylene at 150°C for 10 h over a sil-
ica/alumina-supported zirconium hydride catalysts gave a
100% conversion to saturated oligomers.181 Polypropylene
gave a 40% conversion to lower alkanes at 190°C for 15 h. It
is not clear what use these materials would have, other than
serving as a feedstock for a petroleum refinery.
Ketal structures have been built into cross-linked poly-
mers for cleavage by acid to permit recycling. Compound
14.4 has been used to make cleavable epoxy resins.182
The cured resins can be cleaved by methanesulfonic or
p-toluenesulfonic acids in ethanol. An orthoester has been
cross-linked with a dithiol (14.5), then cleaved to a difunc-
tional monomer suitable for recycling.183
Chemistry of Recycling
14.5
Systems involving ketal and orthoester cleavages may
be too expensive for anything other than specialized
applications.
5. Pyrolysis of Plastics
A few polymers can be converted back to their monomers
for purification and repolymerization. Polymers formed by
ring-opening polymerization fall in this class, as shown in
the foregoing by the conversion of nylon 6 back into capro-
lactam. When ethyl cyanoacrylate is used as a binder for
metal and ceramic powders, it can be recovered for reuse
by pyrolysis at 180°C.184 The monomer can be obtained by
pyrolysis of polymethyl methacrylate in 92–100% yield,185
poly(-methylstyrene) in 95–100% yield, and polytetraflu-
oroethylene in 97–100% yield.186 Polystyrene can be de-
polymerized to styrene containing some styrene dimer by
heating with solid acids or bases at 350–400°C.187 It is pos-
sible that the dimer could be recycled to the next run to pro-
duce more monomer. The best yield ( 99% styrene) was
obtained by passing polystyrene through a fluidized bed of
a solid catalyst at 400–700°C, with a contact time of more
than 60 s.188
Other polyolefins do not depolymerize cleanly to
olefins.189 Sometimes, the pyrolyzate is added back to the
feedstock for a petroleum refinery.190 A pilot plant in Por-
tugal converts plastic waste to fuels and feedstock for a
refinery.191 A municipal plant in Japan converts 6000
metric tons/yr of waste plastic to 2400–3600 metric
tons/yr of heavy oil.192 Many pyrolyses are designed to
obtain a mixture of liquid and gaseous fuels.193 This is lit-
tle better than recovery of energy by incineration of
mixed waste. It is not recycling in the sense of using the
organic material over and over again to make the same or
a similar product.
Pyrolysis of polyethylene and polypropylene for 1 s at
750°C gives mixtures of ethylene, propylene, and butenes
in 91–92% yields.194 Pyrolysis of polypropylene over HY
zeolite gives a mixture of C4–C9 hydrocarbons, mostly
417
monoolefins.195 Cracking of polyethylene over H-ZSM-5
or sulfated zirconia can favor propene and isoalkenes at
high catalyst levels.196 Butenes and pentenes are also
formed. Pyrolysis of mixed plastics in a fluidized bed
yielded a 25–45% gas plus 30–50% oil rich in aromatics,
including benzene, toluene, and xylenes.197 Polyvinyl
chloride interferes with this process by sticking together in
the bed and plugging tubes. Plastics have also been cracked
in vented extruders, the exit gas being washed to remove
hydrogen chloride.198 Catalytic degradation of polyethy-
lene with solid acid catalysts at 400°C produced 8.4% gas
and 90.5% liquid.199 Degradation of polyethylene,
polypropylene, polyisobutylene, and squalane over the ze-
olite H-ZSM-5 produced products rich in gasoline-range
chemicals.200 Feeding molten low-density polyethylene to
a H-Ga-silicate at 525°C gave more than 70% yields of aro-
matic hydrocarbons.201 Heating low-density polyethylene
with MCM-41 zeolite produced a fuel similar to gasoline in
96% yield.202 An iron-active carbon catalyst converted
polypropylene in the presence of a small amount of hydro-
gen sulfide to 98% colorless distillate at 380°C.203
Polyvinyl chloride and polyethylene terephthalate must be
removed from the entering waste.
Heating polybutylene terephthalate with 3 mol% of a tin
catalyst in o-dichlorobenzene converted it to cyclic
oligomers, which might be of value in reaction injection
molding.204
6. Biodegradable Polymers
Biodegradable polymers205 have been advocated by some
to solve litter problems and to offer composting as a way
to dispose of waste plastic. Merely being in a landfill will
not ensure the decomposition of the plastic. During exca-
vation of landfills, the layers have been dated by the dates
on the recovered newspapers.206 Truly biodegradable
polymers, with groups that enzymes can recognize, were
described in Chap. 12. Synthetic polymers such as
418
polyethylene have been made to degrade in sunlight or
fall apart by bacterial action in several ways.207 One is to
put some carbonyl groups into polyethylene, as by in-
cluding a vinyl ketone in the polymerization. Another is
to accelerate photodegradation by inclusion of a metal salt
[e.g., an iron(III) dithiocarbamate], which may be coated
with a material that has to be removed by biodegradation
before the photodegradation will begin. Time control is
obtained by an appropriate choice of metal compound and
its concentration. Starch-filled polyolefins are degradable
in that the bacteria can remove the starch, but the poly-
olefin itself remains. (In the United States the law requires
that the plastic rings that hold six beverage cans together
must degrade in sunlight to avoid animals becoming
caught and dying in the rings.)
Polycaprolactone–paper composites have good resis-
tance to water and are biodegradable.208 Garbage bags of
50:50 potato starch/polycaprolactone are available com-
mercially at about three times the price of polyethylene.209
Larger volume is expected to reduce the cost to twice that
of polyethylene. The Michigan Biotechnology Institute is
developing maize-based coatings for paperboard to replace
polyethylene and wax coatings on paper.210 duPont is pro-
ducing Biomax polyesters, which are modified polyethy-
lene terephthalates, that degrade in composting in about 8
weeks.211 Up to three “aliphatic monomers” are incorpo-
rated into the polyester to provide the linkages for bacterial
degradation. The polyesters are expected to find use as
coatings for paper plates and cups, bags for yard waste, and
such. Eastman sells a biodegradable polyester for use in
film that is made from adipic acid, terephthalic acid, and
1,4-butanediol.212 A biodegradable polyamide that can be
melt-processed has been made by copolymerization of as-
partic and 4-aminobenzoic acids (14.6).213
If a way can be found to make it from ammonia, maleic
anhydride, and 4-aminobenzoic acid, it may be relatively
inexpensive and useful. It could be the biodegradable
equivalent of nylon 6 and nylon 6,6. Chain extension with
bisoxazolines or other reagents in the extruder may be
needed to increase the molecular weight to obtain optimum
physical properties.
14.6
Chapter 14
Biodegradable polymers certainly have a place in the fu-
ture, but with some limitations. If they are on paper that is
being recycled, they will have to be designed to come off in
the process. If they get into streams of plastics being recy-
cled, the recycling could be ruined. For example, starch
would decompose below the molding temperatures of ny-
lon or polyester. If photodegradants enter the waste plastic
stream by this route, the lifetime of the remolded plastic
may be short. It will be difficult to devise a sorting and la-
beling system that will keep the usual synthetic plastics and
biodegradable polymers separate in the waste stream. (A
school system in Virginia decided to use biodegradable
cutlery and trash bags so that they could be composted to-
gether with food waste.214) The best approach may be to
cut back on the use of throwaway items in favor of those
that are durable and last a long time in repeated use.393
D. Rubber
1. Scope of the Problem
The recycling of rubber215 is largely a problem of what to
do with used automobile and truck tires, for they constitute
the bulk of rubber products that are produced. In 1996,
about 250 million tires were discarded in the United
States.216 The “reuse/recovery rate,” which includes burn-
ing for energy, reached 82%, with another 8% being re-
treaded.217 Roughly, the same number of tires were dis-
carded in 1994 and 1995,218 despite that Americans are
driving more miles each year. (Fewer were burned in these
earlier years.) The leveling off in the number discarded
may be due to the increased use of silica with a silane cou-
pling agent as a reinforcement that improves tread life, tear
strength, cut-growth resistance, and ozone aging, while de-
creasing fuel consumption.219 Tires can now last for
100,000 miles, twice as long as they did 20 years ago. The
average scrap tire weighing 20 lb contains 14% fabric, 16%
steel, and 70% rubber.220 The rubber contains carbon black
as a reinforcing agent and is cured with sulfur.221
Rubber tires tend to work to the surface in landfills and
serve as breeding places for mosquitoes when water gets
Chemistry of Recycling 419

into them.222 There are about 800 million used tires in loss in physical properties. The product is cheaper because
stockpiles. Some stockpiles have caught fire and burned for the treated rubber particles cost much less than the raw ma-
months, as at Winchester, Virginia. The best use of a used terials for the polyurethane. The particles can also be used
tire is for retreading. The first retreading increases the life in epoxy resins,237 polysulfides, polyesters, and other poly-
of the tire by 20,000–40,000 more miles.223 Bus and truck mers. The company also uses the surface activation process
tires can be retreaded two or three times, and airplane tires on polyethylene. Perhaps, this can be used in the recycling
as many as 12 times.224 In 1995, 10% of discarded auto- of polyolefin plastics. Another method of surface activa-
mobile tires were retreaded compared with 55–70% of bus tion of rubber particles uses a coating that can cross-link on
and truck tires. A new material that helps prevent delami- curing in a rubber matrix to improve the tensile strength.238
nation of tire treads from carcasses may spur more retread- These rubber particles can be used at up to 100% in mak-
ing.225 About 12 million tires are used each year in civil en- ing conveyor belts, mats, and damping sheets. Energy and
gineering applications, such as retaining walls, artificial equipment costs are reduced because no mixing and calen-
reffs, crash barriers, and floor mats. Drainage pipes that are daring steps are needed.
cheaper than those made of concrete or steel have been
made by strapping tires with steel bands to form the 3. Devulcanization
pipes.226 Old tires split around the middle have been buried
Scrap tires can be devulcanized in a variety of ways.239 The
under golf greens to retain irrigation water longer.227
powdered rubber can be softened with terpenes, then mas-
ticated with chemicals that break the disulfide bonds.240
2. Uses for Powdered Rubber Tires Good physical properties were obtained when the devul-
canized rubber was used at 50–70 parts per hundred of
About 6 million tires are ground each year for a variety of
virgin natural rubber in revulcanization. Similar devulcan-
uses. Coarsely chopped ones are often used in children’s
ization can be done in an open mill with high shearing.241
playgrounds to minimize the impact of falls. They might
However, the recycled rubber had only 50–85% of the orig-
also be used in garden paths, sidewalks, patios, and such.
inal rubber’s tensile strength. Waste rubbers can be devul-
They have also been used as agricultural mulch that does
canized in heated ultrasonic screw extruders in a continu-
not break down so that it does not have to be replaced an-
ous process.242 The product can be reprocessed, shaped,
nually.228 Finely ground materials are produced by cryo-
and revulcanized similar to virgin rubber. The retention of
genic grinding, the fiber and steel being removed in the
mechanical properties is said to be good, the resulting rub-
process.229 Ford and Michelin are planning to use pow-
ber having a tensile strength of 14.2 MPa (about 70% of
dered rubber from tires in new tires.230 A 1991 U. S. law
that of a vulcanizate of natural rubber) and 670% elonga-
specifies the use of powdered rubber from tires in feder-
tion at break. Interchain disulfides may change to cyclic
ally funded asphalt highway paving.231 This is done in
sulfur compounds in the process. Silicone rubber can also
Arizona, California, Florida and Texas, but other states
be devulcanized ultrasonically.243 Reclaimed rubber can be
have yet to follow suit. The increased cost of the as-
used in a variety of products including vehicle mud guards,
phalt–rubber mixture may be the source of some of the
carpet underlays, adhesives, sound insulation, and floor
protests. The price per unit of performance may actually
mats. It was formerly used more with virgin rubber in the
be lower in the long run. Asphalt–rubber mixtures impart
preparation of new tires, but the process gives insufficient
improved low-temperature crack resistance to roads.232
crack resistance in radial tires.244 The crack resistance of
This could translate into fewer potholes in roads in the
such mixtures might be improved by the use of treated sil-
spring of each year and less money spent on patching
ica fillers. The sulfur in finely ground scrap tires can also
them. A road made with 18% rubber–82% asphalt lasted
be removed by sulfur-using bacteria in water over a period
longer and created less noise, 5 dB for cars and 8 dB for
of several days.245 The product can be used with virgin rub-
trucks.233 A study at the University of Detroit suggests
ber to make new tires with improved properties, which are
that 6–7% rubber is optimal.234 For best results, the rub-
cheaper than a tire of all-new rubber. Devulcanized rubber
ber should be ground to less than 80 mesh. Styrene block
might be used to bind coarsely ground rubber into roofing
copolymer rubbers can be used in asphalt to extend the
shingles, insulating board, acoustic board, floors that are
life of the asphalt, up to five times.235
easy on the feet, and other construction uses.
Composite Particles, Inc. uses mixtures of reactive
gases, such as fluorine and oxygen to introduce an oxygen
4. Tires to Energy
functionality, such as hydroxyl and carboxylic acid groups,
on the surface of powdered rubber tires.236 The treated par- Scrap tires can be pyrolyzed to a mixture of gas, oil, and ac-
ticles can be used at up to 40% in polyurethanes with no tivated carbon.246 The zinc and the sulfur stay in the char.
420
The process is being used on a commercial scale on
Hokkaido, Japan, but appears to be uneconomical in the
United States. (Mixtures of scrap tires with waste plastics
have also been pyrolyzed.247) It appears to be cheaper in
the United States to burn the tires for energy at lime kilns,
paper mills, and such.248 The sulfur in the tires must be
trapped by the lime or by other means. The combustion
conditions must be such that the usual thick black smoke of
burning rubber is not present. Recycling the rubber in the
tires to more items of rubber would be preferable to just
burning them as fuel. The real key to fewer tires to recycle
is to devise better land use systems that require fewer auto-
mobiles (see Chap. 15).
E. Metals
1. Methods of Recycling
Aluminum, lead, and steel are the principal metals that are
recycled.249 The aluminum comes mostly from beverage
cans. Of the 130 billion metal cans used in the United
States each year,250 99 billion are made of aluminum.251 (In
1997, 59.1% of the aluminum beverage cans made in the
United States were recycled.252) Cars are the largest single
source of scrap iron.253 The lead is from car batteries. (In
the United States, 96.5% of lead–acid batteries were recy-
cled in 1996).254 Clean streams of metals recycle best.
Non-can aluminum consists of different alloys than the
cans and should not be mixed with them for recycle.
Physical methods of separation are preferred to chemi-
cal ones.255 Magnets are used to separate steel cans from
municipal solid waste. After the battery, gas tank, radiator,
and reusable parts are removed from a used automobile, it
is shredded. Air classification removes the fabrics and light
plastics. The steel is taken out by a magnet. The aluminum
is separated from the copper, zinc, and lead by density us-
ing a sink-float technique, then from remaining materials in
an eddy current separator. If the polyurethane foam is
removed mechanically, the remaining plastics can be sepa-
rated by dissolution in various solvents, acetone for acry-
lonitrile–1,3-butadiene–styrene terpolymers, tetrahydrofu-
ran for polyvinyl chloride, and xylene or cyclohexanone
for polypropylene. This solution process probably suffers
from the disadvantages mentioned earlier in connection
with the use of solvent to separate polyolefins in solid
waste. Much thought is being given to the preparation of
cars that will be easier to recycle at the end of their useful
lives.256 duPont has made a prototype “greener” car in
which polyethylene terephthalate is used to replace many
of the other plastics found in the usual car. Polyester cush-
ions, seat covers, and headrests were used. It says that the
polyester part could be recycled as a unit or remolded in the
Chapter 14
same way that soda bottles are. Steel food containers
should be detinned before melting down, to recover the
valuable tin and to avoid contamination of the batch of
steel. Zinc can be recovered from galvanized steel by dis-
tillation at 397°C at 10 Pa.257 It can also be recovered in
99% yield by extraction with 40% aqueous sodium hy-
droxide at 200°F, followed by electrodeposition of the zinc,
which recycles the sodium hydroxide to the process.258
Steel minimills can operate with nearly 100% scrap
steel to make reinforcing bars for concrete and other items;
in 1999, there were eight steel minimills in New Jersey.259
Scrap provided 56% of the steel in the United States in
1999. The making of steel cans from recycled steel saves
60–70% of the energy needed to make them from iron ore.
Recycling aluminum cans saves 95% of the energy needed
to make them from bauxite ore. Aluminum recycling re-
duces air pollution by 95% and water pollution by 97%,
compared with making cans from bauxite. The emissions
of fluorocarbons from the aluminum fluoride used in the
electrolytic preparation of aluminum are eliminated. The
paper labels and inner and outer coatings are burned off
when the metal is remelted. In contrast to organic materi-
als, such as paper and plastics, the metals can be used over
and over again with little or no loss.
2. Recycling By-Products of the Manufacture of
Metals
When steel is poured from one ladle to another a certain
amount of oxidation of the molten metal occurs. The resid-
ual “kish” can be leached with acid to recover flakes of
graphite, which could supply 6% of the market in the
United States.260 If this leaching is done with hydrochloric
acid, the leachate can be combined with the pickling liquor
that is obtained by dissolving the scale and rust off of metal
sheets. One plant sprays this liquid down a tower 100-ft
high at 640°C (1200°F) to recover iron oxide and hydrogen
chloride for recycle to the process. Some aluminum oxide
and nitride form when aluminum is melted and cast. This
“dross” can be heated to 3000–5000°C in an electric arc
furnace under argon to recover 80–90% of the aluminum in
it.261 The process is said to be 30% cheaper than the current
recovery method. Less “dross” is produced if the argon
plasma is used in remelting aluminum scrap.262 Aluminum
recycling produces a salt slag as a waste.263 Half of this is
a salt flux that can be recovered and recycled. The rest is
impure aluminum oxide that might possibly be combined
with bauxite for the preparation of aluminum. Spent pot
liners in the aluminum refinery can be processed to recover
aluminum and calcium fluorides for recycle to the process
and carbon for use as a fuel.264
Chemistry of Recycling
3. Recovery of Metals from Petroleum Residues
The nickel and vanadium in the fly ash from the burning of
heavy oil can be recovered by chlorination and distillation,
with 67% recovery of the nickel and 100% recovery of the
vanadium.265 Another method is to leach out the nickel
with aqueous ammonium chloride, followed by treatment
with hydrogen sulfide to recover nickel sulfide (in 87%
yield), which could be refined in the usual way.266 The
vanadium was recovered next in 78% yield by solvent ex-
traction with trioctylamine, followed by treatment of the
extract with aqueous sodium carbonate to take the vana-
dium back into water, and finally ammonium chloride to
produce ammonium vanadate.
F. Glass
Most glass recycling267 is done with jars and bottles that
are melted down and made into more jars and bottles. As
with metals, this process can be done over and over again.
Other types of glass, such as windows and light bulbs, as
well as ceramic tableware, have different chemical compo-
sitions and must be kept out of the container-making pro-
cess. They too could be recycled into more window glass
and light bulbs, if there was enough of them in one place at
any given time. The containers must be sorted by color
(clear, green, and brown). If the containers are whole, this
can be done automatically by an on-line color sensor. Bro-
ken glass of mixed colors is a problem, especially if it is in
small fragments, and might have to be diverted to another
secondary use. After sorting by color, the glass is pulver-
ized. Paper labels can be removed by screening or suction.
Steel caps are removed with a magnet. The pulverized glass
(called cullet) can be melted down and made into new con-
tainers. More commonly, additional sand, limestone, and
sodium carbonate are added in making a new batch of
glass. The addition of the cullet lowers the melting point,
saves energy, and prolongs furnace life.
The United States produces 40 billion glass containers
(10.6 million tons) each year. (In 1997, 35% of the glass
jars and bottles made in the United States were recycled,
down from 37.9% in 1996.268) In addition, 800 thousand
tons are imported. Because many of the imported contain-
ers are green wine bottles, too many used green containers
enter the waste stream for effective recycling back into
green containers. Thus, they may have to be diverted to
secondary uses, such as fiberglass and road aggregate.
About 60% of the streets of Baltimore, Maryland, are
paved with glassphalt, a mixture of glass and asphalt. Up to
40% glass can be used in glassphalt. Reflector beads for
roads can be made from recycled clear glass. Auto glass
421
can be converted into bathroom tiles.269 Discarded fluores-
cent light bulbs can be crushed, the mercury and fluores-
cent material removed, and then be converted to fiberglass
insulation.270 This can keep some mercury out of landfills,
but requires an effective collection system for used lamps.
The U. S. Congress has passed resolutions calling for the
Environmental Protection Agency (EPA) to regulate the
disposal of mercury-containing lamps.271 Powdered glass
of mixed colors can be converted to rhodesite, a double-
layer silicate, which is an ion-exchange resin and chemical
adsorbent, by heating with sodium hydroxide or sodium
carbonate solutions at 100–150°C for 1–7 days.272 Pulver-
ized glass has also been mixed with a reactive binder and
compacted into blocks for construction of walls.273 The
blocks serve as insulation that reduces the energy needed
for heating and air-conditioning.
G. Miscellaneous Recycling
1. Composting
Yard wastes (grass, leaves, and tree limbs) constitute
15.9% of municipal solid waste. It can easily be recycled
by composting (see also Chap. 11). The best method is to
eliminate the grass clippings by cutting the lawn frequently
and leaving the clippings on the lawn where they fall. The
leaves can be composted on site, in the backyard, which
eliminates the cost of collection. With the proper moisten-
ing and turning of the pile, odor will not be a problem. Food
wastes can be included if the composter has a screen to
keep out dogs, raccoons, rats, and such.274 Under proper
composting conditions, the decomposition process will
produce temperatures of 56–60°C, which will kill any
pathogens present. Composting can also be done on a
neighborhood or on a municipal basis, although there will
be a cost for collection.275 In Newark, Delaware, the leaves
are raked to the curbside by the homeowner, then sucked
into a city truck for taking to the municipal composting fa-
cility. Many states and cities now prohibit yard waste in the
trash. Texas has 50 large-scale composting operations.276
Brush disposal in Texas landfills has dropped 75% since
1992 owing to them. More than 8000 American farms now
have composting operations.277
Compost can also be produced from a variety of other
organic wastes. Undeliverable bulk mail has been mixed
with food and yard waste for composting.278 Pulp and pa-
per mill sludge can be composted, instead of being put into
a landfill.279 Animal waste from chickens, cattle, hogs, or
other farm animals, can be composted directly or used in an
anaerobic system to produce biogas with compost as a
residue.280 (Contamination of water by pig and poultry
farms is a problem in Delaware, Maryland, North Carolina,
422
and in The Netherlands.) Sewage sludge is often handled in
the latter way. Compost from municipal solid waste has not
worked well, because it may contain toxic heavy metal
ions, slivers of glass, and pieces of plastic.281
Compost consists of the material that does not rot down
readily. The humic and fulvic acids in it are ill-defined, al-
kali-soluble materials derived from lignin.282 They are aro-
matic compounds containing carboxylic acid, hydroxyl
(both phenolic and alcoholic), ketone, and quinone groups.
Incorporation of compost into the soil recycles nutrients;
provides ion-exchange capacity for calcium, magnesium,
and other ions; promotes aggregation of soil particles, wa-
ter infiltration, and water retention. Conventional agricul-
ture depletes soil organic matter to the extent of 50% in 25
years in the temperate zone and in 5 years in the tropics.283
The application of compost from yard waste, crop wastes,
and sewage sludge can enhance the fertility of the soil.
2. Uses for Food-Processing Wastes
Food-processing wastes are often used as food for animals.
Corn gluten meal, left from the preparation of high-fruc-
tose corn syrup, can be used as food for fish in aquacul-
ture.284 Dietary fiber for consumption by humans can be
recovered from pear and kiwi wastes.285 Tomato skins can
be removed by steam and abrasion in a process that elimi-
nates the traditional use of sodium hydroxide for peeling.
The waste can be fed to animals. Brewer’s spent grain has
been used to make bread.286
3. Recycling Wood and Construction Wastes
More wood needs to be recycled. Wooden pallets need to
be reused over and over again. When broken beyond repair,
they can be chipped for use in chipboard,287 or for use in
paper. They can be combined with wood waste from con-
struction or demolition for this purpose. (Frigidaire is now
using reusable polyethylene pallets, which may last
longer.288) New Haven, Connecticut, shreds a combination
of stumps, trees, and other wood waste to produce mulch.
Problems have arisen from burying such waste on con-
struction sites. Sinkholes have formed and methane has
leaked into basements.
Residential construction waste is madeup of 42% wood,
26% drywall, 11% masonry, 4% cardboard, 2% metals, and
15% other materials.289 Roughly 80% of this waste can be
recycled. The key is in segregating the wastes on site. This
can be done by the contractor, the subcontractor, or a clean-
up company. Some scrap lumber can be used as braces, in
the new dwelling. The rest can be handled as in the forego-
ing for chipboard. One way that has been used to keep it out
of the landfill is to put it in a pile at the edge of the site with
Chapter 14
a “free” sign on it. Scrap drywall can be remade into new
drywall. Pulverized drywall can be used as a soil amend-
ment. The ideal is to refurbish existing buildings for new
uses, instead of knocking them down and building new
ones. In some cases, wooden buildings are burned down by
local fire departments as the cheapest way to get rid of
them. The problem is that it costs a lot for hand labor to
take apart a building so that the materials in it can be sal-
vaged. New automated methods for doing this need to be
explored. Perhaps, roofing shingles could be removed by
suction using a mobile crane (“cherry picker”) or by an au-
tomated chisel that would go under the shingles. The old
shingles could be recycled into new shingles or into as-
phalt. After cutting one hole in the roof, hooks on a crane
might pull off a beam or a panel at a time. The nails in the
downed beams could be removed by saws in a machine that
sized up the board by sensors. Masonry might be removed
by a mechanical chisel. It is possible that high-pressure jets
of water could separate the mortar from the bricks after the
wall was taken down. Another possibility would be to use
automatic chisels followed by a planing machine guided by
automatic sensors. Used brick was popular in home con-
struction in the United States at one time. The mortar could
be used in making new mortar, in concrete, or on agricul-
tural soil.
In the United States, 90% of single-family homes are
framed in wood, usually on site (“stick-built”).290 Steel
framing was as cheap as wood, but was used in only 13,000
houses out of 1.3 million built in the United States in
1993.291 The use of steel could help save old-growth
forests, but its production does require a lot of energy.
Preparation of steel framing for houses from scrap steel is
a possibility. In Japan and Sweden, houses are often made
as wall panels in a factory and then lifted into place on site
by a crane. Such a system allows for designs that minimize
waste and centralize what is waste for ease of recycling.
Commercial buildings in the United States are usually
made of steel, concrete, and masonry. Because concrete
made from fly ash from electric power plants is stronger
than that made with sand, this offers an outlet for waste fly
ash. Fly ash can also go into the concrete blocks used in
construction. Wood is also being saved by substituting con-
crete cross ties for wooden ones on railroads. However,
production of cement for concrete is an energy-intensive
operation and trees are a renewable resource when man-
aged properly. Railroad ties made of 100% recycled plastic
are being tested.292
4. Reusing Carpets and Clothing
Textiles are about 5% of municipal solid waste. Their re-
cycling rate is 25%. In the United States 66 million tons
Chemistry of Recycling
is landfilled each year.293 Scrap carpet and used carpet of
polyester or of nylon can be converted back to monomer
for reuse as described earlier. (Seven billion pounds of
carpet is discarded each year in the United States.294)
They can also be used as reinforcing fibers for concrete,
nonwovens, and lower-melting resins, such as polypropy-
lene and polyethylene.295 This might require a surface
treatment of the fiber, or with the polyolefins, the matrix,
to increase polarity. (In former years, textile fibers were
used to produce high rag content paper.) This might be
done to produce strong paper for currency, mailing en-
velopes, and such. Carpet waste has also been converted
into needle-punched thermoformable trunk liners, door
and roof panels for cars, and into panels that can replace
plywood in some applications, such as floors.296 Collins
and Aikman (Georgia) takes back vinyl-backed carpet
from customers and puts it into recycled backing for mod-
ular tile products.297
Similar uses might be found for worn-out clothing.
Clothing that is still useable is collected by charities for
resale.298 The part that cannot be sold in the United States
is shipped to developing nations at the rate of 1 million
containers a year.299 It is then used as such or resewn into
other garments. Recycling textiles generates 37 times as
many jobs as landfills and incinerators.300 Clothing made
of cotton/polyethylene terephthalate can also be recycled
by selectively hydrolyzing the polyester with sodium hy-
droxide, then dissolving the cotton remaining in N-
methylmorpholino-N-oxide for spinning into rayon.301
Presumably, the terephthalic acid could also be recovered
for reuse.
Used mattresses can be resold in 15 states in the United
States after sterilization by dry baking or chemical disin-
fection.302 In other cases, they are sometimes dismantled
and the components sold.
5. Handling Used Oil, Antifreeze, Ink, and Paint
Methods of recycling oil303 were discussed in Chap. 13.
Unfortunately, not all of the oil goes into the recycling con-
tainers. About half of the used oil obtained by motorists
who change their own oil goes down storm drains. Some
cities are putting labels on storm drains pointing out that
anything poured down the drain goes into the nearest river
or lake, in an effort to curtail this pollution. The oil can
harm fish and other aquatic organisms. A year after the
Exxon Valdez oil spill, the effects could still be seen in the
cytochrome P4501A of the fish Anoplarchus pur-
purescens.304 Improperly discarded oil filters release three
times the amount of the Exxon Valdez oil spill into the en-
vironment of the United States each year.305 Oil filters can
be crushed and heated to recover both the steel and the oil.
423
In Delaware, this oil (4500 gal/yr) is recycled at the oil re-
finery at Delaware City.306 Liquid carbon dioxide is being
used to take motor oil off of high-density polyethylene con-
tainers, so that both can be recycled.307 Safety-Kleen Corp.
offers nationwide collection for used oil and antifreeze
from cars and other sources.308 Mobile on-site services are
also available for removing toxic compounds and acid
degradation products from ethylene glycol antifreeze, with
addition of new corrosion inhibitors, so that the antifreeze
can be reused.309 Organoclays have been used to remove
oils from water.310
Ink recycled with the aid of mobile equipment costs
15–35% less than new ink.311 About 60–75% of the recon-
stituted ink is from the waste ink, with the remainder being
new materials to rebuild the ink. A company in Mas-
sachusetts recycles leftover paint by straining it and mixing
it with new paint.312 A company in Toledo, Ohio, heats
paint sludge to 400–580°F, then uses it to make caulks, ad-
hesives, and sealants.313
6. Toner Cartridges
Some manufacturers have taken back used toner cartridges
(used in laser printing), cleaned and inspected them, re-
placed worn parts, if needed, refilled them with toner, and
sold them.314
7. Use of Baths of Molten Metal and Plasma Arcs
When no other way of recycling is available, organic
wastes can be dropped into a bath of molten iron, at
1650°C, to produce carbon monoxide, hydrogen, and hy-
drogen chloride (if chlorine is present).315 Lime and silica
fluxes may be used to form a slag layer. Heavy metals col-
lect in the bath. No nitrogen oxides, sulfur oxides, or diox-
ins are evolved. Destruction of organic compounds is more
than 99.9999%. The synthesis gas formed can be used to
make methanol or for hydroformylation. Any hydrogen
chloride formed would have to be removed by a scrubber.
This is said to be cheaper than incineration.
A plasma arc torch, operating at 3000°F, converts
wastes to hydrogen, carbon monoxide, metal, and a glassy
slag, so that nothing is wasted and nothing goes to the land-
fill.316 The slag can be used in asphalt or concrete. Air
emissions are one-tenth of those of an incinerator. The pro-
cess could make landfills obsolete.
8. Uses for Inorganic Wastes (Other Than Glass
and Metals)
A few examples will be given of efforts to recycle inorganic
wastes. Only 22% of coal fly ash is utilized, with outlets in
cement and concrete products, filler in asphalt, grit for snow
424
and ice control, road base stabilization, and others.317 Con-
crete made with fly ash is stronger and is up to 30–50%
cheaper.318 Building blocks can be made from fly ash, waste
calcium sulfate from flue gas desulfurization, and lime or
Portland cement.319 More could be used if we built our
houses of concrete blocks instead of wood. Efforts have also
been made to recover the aluminum, iron, and other metals
in fly ash. This would reduce the need to mine so much new
ore. As the world switches from fossil fuels to renewable
sources of energy, the problem of what to do with fly ash
will disappear. The ash from incinerated sewage sludge has
been mixed with silica, alumina, and lime for conversion to
tiles and floor panels in Japan.320 Spent bleaching earth
from treatment of edible fats and oils presents a disposal
problem.321 The best approach is to regenerate it for reuse.
Extraction with isopropyl alcohol or hot water under pres-
sure removes adhering oil so that the solid can be reused as
a filter cake. It can also be put into a cement kiln or used in
land application. Contaminated sulfuric acid can be cleaned
up by cracking at 1000°C, followed by conversion of the
exit gas to fresh sulfuric acid.322 The process is in use at
three plants in Europe and at six in the United States. Zero
discharge of wastewater is the goal of industry. This in-
volves biological treatments, reverse osmosis, and so on.
The color of spent dyebath water can be removed by treat-
ment with ozone so that the water can be reused.323
III. METHODS AND INCENTIVES FOR
SOURCE REDUCTION
A. Range of Approaches
The following hierarchy of methods of use goes from the
ones with the most waste to the ones producing the least
waste: (An example is given in most cases.)
Use once, then bury it in a landfill (throwaway packag-
ing).
Use once, then compost it (biodegradable packaging).
Use once, then burn it with recovery of energy (throw-
away packaging).
Use once, then make into a different object, which after
use can be burned or buried (high-density polyethy-
lene milk jug made into a container for motor oil).
Use once, then make into a different object that will last
for many years (polyethylene terephthalate soft-
drink bottle made into fiber for clothing or a sleeping
bag).
Use once, melt, and reshape to original use (recycled
aluminum cans or single-use glass bottles).
Use once, melt, and reshape to a different long-term use
(steel can made into reinforcing bar for concrete).
Use once, hydrolyze the polymer to recover the raw ma-
terials; which are then converted into a duplicate of
Chapter 14
the original object (polyethylene terephthalate soft-
drink bottle made into another soft drink bottle).
Use 10–60 times, then remake into a duplicate object
(refillable glass or polyethylene terephthalate soft-
drink bottle).
Use 10–60 times, then remake into a different object
with a long life (polycarbonate milk bottle recycled
into a part for an automobile).
Use repeatedly, sharpen as needed, replace small parts
that wear out (saw, safety razor).
Use indefinitely (china mug or drinking glass).
Is the object or its content needed at all? (bottled water,
neckties)
B. Making More with Less Material
The best approaches are to reduce, reuse, or recycle, listed
in order of decreasing importance. To a manufacturer,
source reduction324 often means making the same number
of objects with less material. This may be a design change,
such as substituting an indented bottom for the polyethy-
lene base cup formerly used on polyethylene terephthalate
soft-drink bottle. The use of a stronger plastic resin, per-
haps with a higher molecular weight, or a better molecular
weight distribution, may allow the bottle to be made thin-
ner. Optimization of biaxial orientation may lead to in-
creased strength, so that less material is needed. In 1978, a
2-L soft-drink bottle of polyethylene terephthalate weighed
100 g and cost $0.48. Today, it weighs 50 g and costs
$0.10–0.12.325 The milk jug of high-density polyethylene
of the early 1970s weighed 95 g. In 1989 it weighed 60
g.326 The 12-fluid–oz. aluminum beverage can has become
thinner over the years until now 32 cans weigh 1 lb.327 This
represents a 50% reduction in weight. The pressure in the
can helps it to hold its shape. Another method of reduction
is to achieve longer wear (see Chapter 13). Because of im-
provements in the materials and methods of construction,
automobile tires now last twice as many miles as they did
20 years ago.
C. Throwaway Items and the Consumer
Source reduction for the consumer means obtaining the
products that he or she needs with a minimum of waste to
be discarded. The most important approach is to substitute
reusable objects for single-use, throwaway ones. It is in-
structive to compare what is done today in the United
States with what was done 50 years ago and with what is
still done in many other countries392 (Table 14.2).
Too many items are discarded because a person wants
something new; a fad passes, and an item goes out of fash-
ion; the person gains or loses weight; the child outgrows it;
Chemistry of Recycling
Table 14.2 Approach to Substitution of Reusable Objects for Throwaways
Today
Paper napkin
Paper tissue
Plastic bag for waste
Discard broken shovel and buy a new one
Single-use soft-drink container
Single-use polyethylene milk jug
Single-use glass cider jug
Assortment of two dozen screws in plastic
container
Discard faulty toaster
Two disposable mouse traps in plastic
package
Bottled water
Disposable polystyrene cup
Disposable diapers
Disposable camera
Disposable razor
Aluminum pan under frozen TV dinner
Cling wrap and aluminum foil to wrap food
Plastic grocery bags
Weed whacker or herbicide
Recreation vehicle
Disposable needles for syringes
Electric pencil sharpener
Photocopier
One car per driver
Disposable ballpoint pen
Leaf blower
it was stored improperly; a minor repair or refinishing is
needed, and so on. It should be possible to reverse some of
these trends to minimize waste, energy consumption, and
natural resource depletion without adversely affecting
health or longevity of people. One-third of Americans to-
day are obese, in part because of all of the “labor-saving”
devices to which they have become accustomed.
There is some question over why some of the items in
Table 14.2 need to be disposable. Two billion disposable
razors are used each year in the United States. Reusable
safety razors work, with the need to dispose of only used
blades. This author has minimized his use of razors and
shaving cream, while saving 10 min every day, by wearing
a beard. Kodak advertises its single-use camera as 86% re-
cyclable. A regular camera lasts so long that recycling is a
minor issue. It requires only new film. The use of wooden
pencils has resulted in overexploitation of red cedar (Ju-
niperus virginiana) trees and more recently of Libocedrus
decurrens.328 Pencil board can be made today from recy-
cled paper.329 A mechanical pencil requires only replace-
425
What was formerly done
Cloth napkin
Handkerchief
Wash out garbage can
Replace broken handle on shovel
Glass bottle with $0.02 deposit
Milk delivered to door in refillable glass bottles
Take own bottle to farm for cider
Buy one screw at local hardware store
Local repair of toaster
Buy one mouse trap and use it for years
Canteen
China cup or drinking glass
Cloth diapers collected from home and cleaned by
diaper service
Use camera indefinitely, just buy new film as
needed
Safety razor used indefinitely, just buy new blades
Use own pan repeatedly
Wax paper
Paper grocery bags or market basket
Hand clippers
Tent
Sterilize needles in autoclave
Turn sharpener by hand
Copy by hand or blue print
Ride bus or street car
Fountain pen
Rake
ment leads, which are used completely. A fountain pen re-
quires only replacement ink. A cutout hole eliminates the
need for a plastic window in an envelope. A rubber stamp
or a fountain pen eliminates the need for an adhesive return
address label. A moist sponge can eliminate the need for
the strip of adhesive tape sometimes used to seal envelopes.
If the material inside is not personal, the flap can just be
tucked in. An air-cooled engine requires no engine coolant.
Alliance Medical Corporation cleans used surgical in-
struments, sterilizes them, and sells them to hospitals at a
discount.330 Before the 1970s hospitals did this themselves.
A few stores sell secondhand building materials, such as
doors, kitchen cabinets, and carpets.331 Since 1992, a
church in Wilmington, Delaware, has run a warehouse for
used building materials, such as kitchen sinks, that are do-
nated by local businesses, contractors, and families remod-
eling their homes. It provides help to low-income families
that are improving their homes.332
Some wasteful practices are part of local customs. There
is no need to buy shoes for a child who cannot walk. Many
426
stores in the United States do half their annual business in
the month before Christmas. Many of the presents given
are ill-chosen and unwanted. Some people consider Christ-
mas—a religious observance—to be overcommercialized.
The same is true of many wedding presents. Would a gift
certificate at a local grocery store be a suitable replace-
ment? Synthetic Christmas trees can be used year after year
without having to cut a tree in the forest. This is probably
more environmentally sound than “recycling” a real tree by
chipping it for use as mulch. One waste disposal firm in
Delaware distributed 1000 free plastic bags for handling
the used trees, thus adding plastic to the waste stream.333
Some stores replace their storefronts well before they are
worn out because this brings in more customers and sales
go up.334
Instead of having your own of everything, could you
share a tool with neighbors, borrow it from a civic associa-
tion, rent it when needed, or hire a person with one to do the
job? As an example, a person with a 1/2-acre lot probably
does not need his own chain saw. There is a small move-
ment in this direction. There are 200 sharing villages in
Denmark, where 10% of all new housing is in cohousing
clusters, which use half as much land as the usual sub-
urb.335 Some cohousing communities share tools, such as
staple guns, sewing machines, leaf rakes, carpentry tools,
toilet plungers, backpacks, or tents. A system of car shar-
ing is developing in Europe. Could you spend a little more
for a washable wall paint so that you would not have to re-
paint so often? Is the deck really necessary, or could you
use a lawn chair? Houses being built in the United States
today are larger and average fewer occupants in them than
those built a generation ago. Millions of people, including
14 million widows, live alone in houses in the United
States. Is there a way that we can alter our social system so
that more of these singles can share a house?
D. Containers and Packaging
Containers and packaging336 constitute 34% of municipal
solid waste by volume. There are many ways that this can
be reduced without lowering standards of sanitation. More
businesses are shifting to multitrip containers for deliver-
ing their products.337 In one case (Nalco), the use of 96,000
15 to 800-gal stainless steel containers has eliminated the
need to dispose of 3-million drums and 30-million lb of
chemical waste since the program began.338 Use of return-
able, refillable, pesticide containers reduces the likelihood
of contamination of the environment, while saving time
and money.339 Manufacturers ship more than 90% of all
products in the United States in corrugated cardboard
boxes.340 Multitrip containers for the delivery of food to
supermarkets could save large amounts of corrugated card-
Chapter 14
board. This calls for some innovation to produce easy-to-
open and close containers that nest or can be collapsed for
reshipment to the manufacturer. Standardization of pack-
age sizes or at least crate sizes could allow them to be used
by many different companies with credit going to the com-
pany that provided them in each specific case. A German
manufacturer is studying the use of collapsible polypropy-
lene crates for use with its products. These might be made
of plastic or other material. 3M has a reusable, collapsible-
packaging system that saves the company $4 million/yr.341
Frigidaire has a similar program.342
There are also many opportunities for reduction of pack-
aging at the consumer level. The Giant chain of supermar-
kets in the eastern United States offers over 100 different
foods and other items in bulk (in addition to the usual fruits
and vegetables). The customer uses a scoop to fill a plastic
bag, then puts a sticker and a plastic tie on it. The items in-
clude cereals, candy, dried fruits, nuts, pasta, snacks, and
pet supplies. They are usually cheaper than those that are
prepackaged. Unfortunately, this is only a small portion of
the items sold in the store. It should be possible to add
beans, detergents, coffee, and other items. Beverages might
be dispensed into the customers own container, as done
with milk in parts of Germany. The only requirement may
be that the cashier at the checkout counter be able to rec-
ognize the item inside the bag or jar. Cereal in large boxes,
instead of in individual variety packs is 78% less expensive
and generates 54% less waste.343 Buying fruit juice in
frozen concentrate, rather than in shrink-wrapped packs,
cuts the cost 41% and the waste 61%. The least packaging
for breakfast cereal uses the form-and-fill package made of
plastic film, and uses no outer box. The box of rolled oats
used to be made of all paper. Now it comes with a plastic
top, which makes it harder to recycle. Some bread is dou-
ble-wrapped, even though a single layer is sufficient. Some
fabric softeners are now available as liquid concentrates.
The customer buys the original container, which can then
be refilled with concentrates as needed. There are also ex-
amples in which small items are put into oversized pack-
ages so that the package can carry an advertisement. It
would be better to put the advertisement on the bin where
they are kept.
Beverage containers account for over 5% of municipal
solid waste. As mentioned earlier in this chapter, the
United States uses 99 billion cans and 46 billion glass con-
tainers each year. David Saphire of Inform, Inc. has done a
careful analysis of the use of refillable containers for this
purpose.344 Refillable glass or polyethylene terephthalate
bottles making 25 trips use 91–93% less material and lead
to 96% fewer bottles as waste. Even at eight trips, refillable
glass bottles use 78% less glass than one-way bottles car-
rying the same amount of beverage. At 25 trips, glass beer
Chemistry of Recycling
bottles will consume 93% less energy than would be re-
quired to make the single-use bottles to carry the same
amount of beverage. The energy used in washing the refill-
able bottles is more than offset by the energy that would be
required to make new bottles. A 12-oz. refillable bottle
used ten times takes 75% less energy per use as a recycled
glass or aluminum container and 84–91% less than a
throwaway one.345 Consumers might be surprised if they
knew what they throw away in the cost of packaging for
single-use containers. The cost of the 2-L polyester bottle
of a soft drink is $0.10–0.12, which amounts to 14% of the
$0.78 price per bottle. (The price will vary with the store
and with the brand. This was the lowest price found in a su-
permarket in Newark, Delaware, in September, 1997.) A
typical aluminum beverage can now sells for $0.057,346
which is 29% of the $0.20 price of the container filled with
a soft drink. The cost of the glass jar for baby food may
amount to one-third of the purchase price.347 An alternative
that saves money and reduces waste is to mash the food
yourself or to puree it in a kitchen blender.
Polyethylene terephthalate bottles are not refilled with
beverages in the United States for fear of contamination.
After soaking with benzene, butyric acid, malathion, and
lindane for 2 weeks at 40°C, only part of the contaminants
could be removed by 8% aqueous ethanol.348 Sophisti-
cated gas chromatographic headspace analysis is used to
reject contaminated bottles in Europe where they are re-
filled with more beverage. The refillable polyester bottle
is heavier than the single-use one. Use of a barrier coating
of silica or other material to prevent contaminants from
contacting the polyester might solve this problem for the
United States (see later.)348a Brief treatment of the interior
of the bottle with fluorine at the time of manufacture
might work. This method is used with polyethylene tanks
for gasoline that are used on automobiles. The problem of
scuff marks from repeated use that detract from the ap-
pearance of the container might be solved by a hard-sur-
face coating, such as the cross-linked acrylic coatings
used on plastic automobile headlights. The ideal coatings
would not interfere with the recycling of the bottle at the
end of its useful life. Polyethylene naphthalate softens at
a higher temperature, is harder to scratch, and is a better
oxygen barrier, which extends the shelf life for beer.349 Its
use in blends with polyethylene terephthalate in beer bot-
tles could complicate recycling, unless a good marking,
deposit, and refund system is developed. Coating the in-
side of the polyethylene terephthalate bottle with a 0.1-
m layer of hydrogenated carbon, doped with nitrogen
using a plasma at less than 50°C reduces oxygen transport
by 30-fold.350 This may eliminate the need for the
polyethylene naphthalate beer bottle. Such a coating
might make it possible to refill polyethylene terephthalate
427
bottles for soft drinks repeatedly in the United States.
Polyester bottles must be washed with less alkaline deter-
gents than those used with glass bottles, to avoid hydrol-
ysis of the polymer. The use of enzyme-containing deter-
gents at lower temperatures should help.
It may be possible to devise a refillable aluminum can
for beverages. It could be shaped like the aluminum bottles
that laboratory chromatographic alumina is shipped in.
Milk and orange juice are also sold in 1/2-gal bisphe-
nol A polycarbonate jugs. A jug may cost $1.10, but the
cost per trip is low when spread over 40–60 trips.351 A de-
posit of $0.25 ensures a high-return rate. Some 8-fl oz.
school milk bottles of polycarbonate realize over 100
trips. Just as with the polyester bottles, these also have to
be washed under mild conditions to avoid hydrolysis. At
the end of their useful life, the manufacturer (General
Electric) takes back the bottles for remolding into bottle
crates and such. This system has been used in the United
States, Sweden, and Switzerland for over 10 years. Most
milk is sold in paper cartons coated with polyethylene, or
in jugs made of high-density polyethylene. The system for
milk requiring the least packaging is probably powdered
skim milk equivalent to 22.7L (24 qt) of liquid milk in a
cardboard box covered with aluminum foil. It can be
stored at room temperature and requires refrigeration only
after it is made up as liquid milk. The polycarbonate bot-
tle cannot be used for soft drinks because it is not a suit-
able barrier to carbon dioxide. A challenge is to find a
suitable barrier that will not interfere with recycling the
container at the end of its useful life as a bottle. An inor-
ganic barrier coating, such as silica, might work.
The average American consumes 54 gal of soft drinks
each year. This is more than the amount of water that he or
she drinks. For comparison, the average American drank
20.4 gal of coffee in 1996,352 and also consumed 152 lb
of sugars each year. About one-third of this comes from
soft drinks, which use sucrose or high-fructose corn syrup
or both. Both promote dental caries.353 A typical soft
drink contains 10–14% sugar, 0.37% flavoring, and
0.185–0.74% citric acid in water saturated with carbon
dioxide.354 It may also contain color, caffeine, and preser-
vatives, such as sodium benzoate. Phosphoric acid and
other acids may be used instead of citric acid. The pH be-
fore carbonation is 2.35–2.66. It contains no vitamins, min-
erals, protein (usually), fiber, or complex carbohydrates. Its
consumption at such levels raises serious nutritional ques-
tions. If other beverages were substituted for it, container
waste would drop.
Bottled water is popular in the United States today.
Some people feel that it tastes better, has fewer impurities,
and may confer higher social status than tap water.355 Anal-
ysis of 37 brands in 1991 found that 24 had one or more
428
values that were not in compliance with the drinking water
standards of the United States.356 Some were just bottled
municipal water. Testing of 1000 bottles of 103 brands in
1999 found that about “one third of the brands had at least
one sample containing levels of contamination that ex-
ceeded state or industry limits or guidelines.”357 Bottled
water does not contain sufficient fluoride ion for good den-
tal health.358 It would be better to drink at the nearest water
fountain or to fill your reusable bottle there. This would
eliminate some plastic container waste. (Bottled water does
have a place in some of the less-developed countries in
which the standards of sanitation may be inadequate to pro-
tect the public water supply.) One company uses refillable
bottles of polyethylene terephthalate for its mineral water
in Holland and Belgium.359 The headspace of returned bot-
tles is checked by gas chromatography–mass spectrometry
at the rate of 0.1 s/bottle. The label is cut off with a high-
pressure water jet at the rate of 550 labels per minute. The
sleeve waste is recycled. The bottles are cleaned at 167°F,
inspected physically, filled, and a new shrink label of
polyethylene applied. The crate of six 1.5-L bottles has a
deposit of $7.20, half for the crate and half for the bottles
(i.e., $0.60/bottle). The return rate is 94%.
E. Using Less Paper
The United States consumes enormous amounts of paper
each year, 1.5 tons/household per year.360 It takes 5 billion
ft3 of trees plus 35 million tons of recycled wastepaper to
make this paper. Each year Americans receive 4 million
tons of junk mail, 47% of which is discarded by the recipi-
ent without looking at it.361 It took 1.5 trees for the junk
mail received at each household. Each U. S. office worker
discarded 225 lb. of paper in 1988.362 Various methods
have been suggested for reducing office waste, such as us-
ing both sides of the page, using smaller sheets for short
memos, using e-mail, circulating memos instead of making
copies, eliminating coversheets and wide margins, or mak-
ing fewer photocopies. New incentives are needed for mak-
ing fewer photocopies and reducing the number of com-
puter printouts. (Charging individuals more for each one
might help.) Various predictions of a cashless society
where transactions would be done by computer and e-mail
have been made in the past. This is just starting to happen.
Use of e-mail for bank statements and other investment in-
formation would reduce the volume of mail. If every home
with a television set could use it for this purpose, the vol-
ume of paper used in mail would be reduced. This may re-
quire further developments in technology. A shift from pa-
per packaging back to dishes of china at fast-food
restaurants could reduce the use of paper. The restaurants
would have to install more dishwashers. A surcharge on pa-
Chapter 14
per dishes and wrappings for take-out food might encour-
age more customers to eat on-site and might reduce litter
along roads.
Because newspaper is such a large component of house-
hold paper, it deserves special consideration. It can be re-
placed by a system that transmits the information in the
newspaper to the customer over the telephone lines during
the night. In the morning, the customer queries the terminal
to obtain the table of contents. He might also print out the
portions of interest. When such systems have been test-
marketed, they have flopped. One problem may be that
they cannot be taken to the office to be read at lunch time.
A standard command on the terminal to print out the front
page, the sports scores, and the stock prices, or whatever
else was of special interest, might take care of this. It is also
possible that the system was tried before people became
used to the World Wide Web and similar systems. Updat-
ing the news sections hourly might be a selling point with
some customers. Some scientific journals are now on-line.
Popular magainzes might be handled in the same way. This
would eliminate the need for finding space for them in the
home and the need for finding a place to recycle them. It is
also possible to read them at a central library, either in per-
son, or through a web site. Sharing with friends is a good
way to use magazines that contain no time-sensitive
material.
When the price of newsprint has risen, newspapers
have gone to lighter, thinner paper, and have reduced the
sizes of margins. Newsprint is a relatively weak paper
made by grinding the tree and bleaching the product. This
is a thermomechanical pulp, in contrast with writing paper
where the lignin is removed by chemical means. The chal-
lenge is to find a dry strength additive for paper that will
produce a thinner, stronger paper that will not cost any
more than current newsprint. This may also involve find-
ing an inexpensive additive to increase opacity, because
thinner paper might allow print on one side to be seen
from the other. Smaller headlines, type, and margins
would reduce the number of pages in the daily newspaper.
However, smaller type is harder to read. Neither the
newspaper nor its readers may want to go to a more con-
cise writing style to save paper and the cost of it. Limit-
ing the size of advertisements could save a lot of space.
This could be done as a matter of policy or by increasing
the rates for the larger ads. It might also be done by gov-
ernment regulation or a tax on the larger ads. The problem
is that advertisements support most of the newspaper. Ad-
vertisers might seek other media under these conditions.
Customers would probably not buy many newspapers
without advertisement because of the much higher price.
If the cost of the newspaper was determined by the num-
ber of sections bought, people might buy fewer. Some
Chemistry of Recycling
might opt for only the international and national news,
plus the sports section. Other might be content with just
national and local news without the sports, business, real
estate, and automotive sections. This could reduce the
price and amount of paper used by as much as 50%. It
would require the development of more complicated
vending machines for newspapers. It would be instructive
for Americans to see what is done in countries where
newsprint is less plentiful and more expensive.
F. Life-Cycle Analyses
Life-cycle analyses363 are becoming increasingly popular
(see Chap. 17 for more details). They consider the
amounts of energy and materials used, together with the
waste and pollution produced, in taking a product from
cradle to grave. Unfortunately, they are not all done in the
same way or with the same assumptions. Most assume the
use of energy from fossil fuels, rather than from renew-
able sources. Very few consider the costs of global warm-
ing and natural resource depletion, not to mention the loss
of biodiversity. It is important to see what assumptions
have been made and who paid for the study, for it may not
be one that is completely objective. The use of paper ver-
sus polystyrene for cups may tend to favor the foamed
polystyrene one unless a china mug or a drinking glass is
included.364 The reusable one will win because washing it
is not very expensive and does not involve the energy and
materials to make a new one. Paper versus plastic is also
debated for grocery bags. The winner here is the string
bag or market basket that the customer brings to the store.
Some paper bags have a statement on them that they are
recyclable and are made from a renewable resource. Some
also say, “reuse this bag for 2 cents credit.” Apparently,
this not enough of an incentive for customers, for very
few of them do it. (Customers could also bring back for
reuse the thin polyethylene film bags used to carry and
store fruits and vegetables.) A local supermarket has used
bags of high-density polyethylene with labels which say,
“Save trees! By using plastic bags, you help save the trees
and forests that are cut each year to make paper bags. Re-
cycle! Help the environment.” This is encouraging the use
of a nonrenewable resource. It also ignores the fact that
the recycling of plastic films is not working well. A thin
plastic bag closed by heat-sealing, a clip, or a paper or
plastic tie might replace the shrink-wrapped polystyrene
tray. Trays and egg cartons were once made of paper, a
renewable resource, by pulp molding, the way they used
to be. One company has been “earning greenie points” by
packaging its toaster ovens in a molded pulp made from
100% used newspapers.365 This replaced foamed
polystyrene.
429
G. Ecolabels
Ecolabels366 designed to influence consumers choices are
popular. A label attached by a pressure-sensitive adhesive
to a plastic film around papers in the mail said, “The plas-
tic cover (polyethylene) is not damaging to the environ-
ment. It can be recycled, is nontoxic, and requires no more
energy to produce than recycled paper. It helps both to re-
duce costs and the number of returns.” Some advertise-
ments have arrived in white low-density polyethylene en-
velopes with a pressure-sensitive adhesive seal and a label
attached with a pressure-sensitive adhesive, together with
the chasing arrows sign and the message, “This bag is re-
cyclable.” It implies that the adhesives and the paper in the
label will not hurt the ability to recycle it. This is question-
able, but may depend on the process used. If the paper is
left in, it may produce weak spots in the new plastic, be-
cause it will not adhere well to the polyethylene and may
decompose at the temperature of remolding. The reuse is
limited to pigmented materials and cannot be used to make
clear plastic. Even the American Chemical Society has
shipped two magazines together in clear low-density
polyethylene with the chasing arrows marked with “100%
recyclable.” While the film was heat-sealed around the
magazines, a paper label was held on by a pressure-sensi-
tive adhesive. One journal has arrived at the author’s home
with a separate sheet of paper inside the heat-sealed enve-
lope. The sign on the paper sheet said,” Recyclable plastic.
Please recycle.” The address was on a paper label attached
to the sheet of paper by a water-moistenable adhesive. An-
other such bag even specified in the label on the plastic,
“minimum 30% industrial content—minimum 15% post
consumer content.” Another magazine arrived with the
sheet of paper inside a biodegradable plastic bag. The ad-
dress was on a paper label attached by a water-moistenable
adhesive. The message on the piece of paper was, “Printed
with soy ink. Printed on recycled paper.” There are simpler
ways to handle magazines in the mail. The journal Science
uses a paper label attached by a water-based adhesive at
one corner of the front. The system using the least material,
and among the easiest to recycle, was found on a May 1997
issue of the magazine Horticulture. The address was
printed on a white rectangular space at the bottom of the
cover using an ink-jet printer. It might be possible to use
ink jet printing with a nontoxic edible ink to mark oranges,
bananas, and other foods, instead of putting a plastic sticker
on each one. Ink-jet printing can also be used to label bot-
tles to replace the shrink-fit labels of a different plastic than
that in the bottle. Further development may be needed to
make them as colorful as the current shrink labels. Refill-
able bottles can also use painted or embossed labels so that
no new one is required when the bottle is reused. The lib-
430
eral use of the term “recycled” can be misleading. It has al-
ways been good manufacturing practice to put scrap made
in the plant back into the process. Today, a lot of it is being
called recycled. It would be better to reserve the term for
postconsumer material that has been reused. Very few
products are made from 100% postconsumer waste.
H. Ecoparks
An ecopark is envisioned as a place where everything that
goes into the system emerges as useful products. The waste
of one industrial plant is used as starting material for an-
other. The outstanding example is in Kalundborg, Den-
mark.367 The electric power plant sends steam to the Statoil
refinery, to the Novo Nordisk plant, and to the town for
heating buildings. It also burns some gas that the refinery
would otherwise flare. Excess heat also goes to a fish farm
that produces 250 tons of fish each year. Ninety percent of
the energy in the coal is used. Sulfur dioxide from the
scrubber on the power plant is converted to calcium sulfate
for the production of drywall. The drywall plant also uses
gas from the refinery that would otherwise be flared. Sul-
fur removed from oil at the refinery is converted to sulfuric
acid for use at a plant 50 km away. The fly ash and residual
ash from the power plant are used in cement and roads.
Sludges from the fish farm and the enzyme plant of Novo
Nordisk are used as fertilizers. All of this collaboration oc-
curred without government action, unless one includes the
effects of government regulations. There is also an indus-
trial partnership in southern Ontario, where calcium sulfate
from scrubbing the flue gas of a power plant is made into
drywall and the waste heat from generating the power is
used for growing vegetables in 8 acres of greenhouses.368
An ecofarming project on Fiji is also trying to use every-
thing.369 Brewery waste, which used to be dumped into the
harbor (and damaged the corals), is mixed with rice straw,
sawdust, or shredded newspaper for use as a substrate for
the growth of mushrooms. The residue from the mushroom
culture is fed to chickens. The chicken waste is used to pro-
duce biogas. The residue from the biogas generator be-
comes fertilizer for the fish pond. Vegetables are grown hy-
droponically on the top of the fish pond.
I. Economics of Recycling
Some authors feel that recycling does not make sense eco-
nomically.370 They cite high collecting and sorting costs.
They also point out that a pricing mechanism is needed that
reflects the true social cost, including resource depletion
and environmental damage. Others feel that recycling is
economically viable today.371 Recycling creates more jobs
than landfilling or incinceration.372 In Seattle, the average
Chapter 14
cost to dispose of a ton of nonrecyclable municipal waste in
1995 was 105 dollars. The average cost to collect and pro-
cess a ton of recyclables was 28 dollars. One way that has
been found to reduce the amount of municipal solid waste
is unit pricing, a “pay as you throw” policy.373 This can
take the form of stickers that have to be purchased and
placed on each bag of trash (as in Ithaca, New York) or
stickers on each bag more than one. (For more on environ-
mental economics, see Chap. 17.)
J. The Role of Government in Reducing
Consumption
It is apparent that source reduction and higher recycling are
unlikely to happen without some form of government in-
tervention.374 This can take the form of laws banning cer-
tain uses, taxing undesired practices, subsidizing desirable
practices, labeling laws showing true costs, or other such.
Thus, it is possible to consider taxes on throwaway items
and those based on nonrenewable raw materials, such as
petroleum, natural gas, and coal. Denmark’s tax on waste,
started in 1987, is the highest in Europe.375 Austria, Bel-
gium, Finland, France, the Netherlands, and the United
Kingdom also tax waste. Sweden and Norway are consid-
ering such taxes. The U. S. Congress is studying the re-
moval of the hundreds of billions of dollars of subsidies
given each year to virgin resource producers.376 These sub-
sidies to the mining, timber, and petroleum industries are
considered to be impediments to recycling. Maine has a
law requiring disposal fees paid at the time of purchase of
major new appliances, furniture, bathtubs, and mat-
tresses.377 There are also laws that require a minimum re-
cycle content in new items.378 Sweden and Germany have
banned unsolicited direct mailings.379 If the U. S. Postal
Service would require first-class postage, the amount used
on personal letters, for junk mail, the amount of such mail
would decrease.
The 65%-recycling rate for aluminum beverage con-
tainers in the United States in 1994 is considered high.380
However, if one looks at the billions of cans that are lost
from the recycling loop each year, it is easy to see that a
better system is needed. There is a proven way to obtain
more of them back. Saphire has reviewed the role of de-
posits in retrieving used beverage containers.381 Maine re-
demption rates for beer and soft-drink containers are 92%,
for wine containers 79%, for juices, and for other noncar-
bonated beverages 75%. In most of the other eight states
with deposit legislation, only beer and soft-drink contain-
ers are covered. New York has the lowest redemption rate
of the states with bottle bills, with a redemption rate of 66%
for soft drinks and 79% for beer. Delaware’s bottle bill is
relatively ineffective, because aluminum containers and
Chemistry of Recycling
2-L plastic containers are exempted. British Columbia is
considering expansion of its 27-year-old bottle bill to cover
sports drinks, bottled water, fruit and vegetable juice, wine,
and spirits.382 Higher rates of return can be obtained with
larger deposits, as shown by the use of $0.25 per container
for some milk containers, as mentioned earlier in this chap-
ter. A nationwide bottle bill with the coverage of that in
Maine and with higher deposits than those now used in bot-
tle bill states would increase recycling greatly and provide
more jobs at the same time.
Michigan’s bottle bill resulted in 4684 new jobs in the
state. A tiered system with the payback of the full deposit
for a refillable container, half back for a one-way container
that can be recycled, and none for a one-way container that
cannot be recycled has been recommended. Requiring the
use of standardized (generic bottles), as done in Germany,
also helps. Any bottler can use any other bottler’s bottles
just by putting on a new label. Efforts can be made to make
recycling of containers as convenient as possible by the use
of reverse vending machines. Deposits on jam jars, deter-
gent bottles, or others, may also reduce waste. Denmark
and Prince Edward Island have outlawed nonrefillable con-
tainers for beer and soft drinks. The return rate in Denmark
is 98%. However, beverages exported by Denmark are in
throwaway containers. In the grocery stores in the United
States, an item for purchase must be marked not only with
the price of the packaged item, but also with the cost per
unit weight or unit volume. It might be appropriate to re-
quire also the cost of the container per use. This would
show the economy of using refillables.
Germany is further along than other countries in making
manufacturers responsible for the ultimate recycling or dis-
posal of what they produce. A 1991 law requires that com-
panies either collect their own waste packaging for recy-
cling or pay fees to Duales System Deutschland to do it for
them under the “Green Dot” system.383 In 1994, the recy-
cling fees were highest for plastic (Table 14.3).
The system is working, but not without some growing
pains. In 1997, 5.6 million metric tons of used packaging
materials were collected, which was 89% of that used. The
recycling rates were glass 89%, corrugated cardboard 93%,
plastics 69%, composites 78%, aluminum 86%, and tin-
plate 84%.384 Other European countries have complained
that they have been inundated with material for recycling
from Germany. Pyrolysis of plastic waste to produce oil
and gas for fuel has been used, but really should not be
called recycling.385
The European Commission has proposed a takeback law
covering electronic equipment, including appliances, of-
fice machinery, and telecommunications equipment. 386
(For more on how public policy can influence the environ-
ment, see Chap. 18.)
431
Table 14.3 Recycling Fees for
Containers in Germany
Component $/kg
Plastics 1.97
Composites 1.40
Beverage cartons 1.13
Aluminum 1.00
Tinplate 0.37
Paper 0.33
Natural materials 0.13
Glass 0.10
IV. THE OVERALL PICTURE
For a sustainable future, more things will have to be made
from renewable resources and fewer from nonrenewable
resources. This means using paper instead of plastic wher-
ever possible, unless the plastic is based on a renewable
source (as described in Chap. 12). The throwaway habit
must be thrown away in favor of reusable objects, de-
signed for long life, easy repair, and ease of recycling of
the materials in them. Objects made of 100% postcon-
sumer waste must become common, instead of being rare
as they are today.
No one has found a way to curb the overconsumption of
the industrialized nations. (E. O. Wilson pointed out that if
all nations used materials at the same rate as the United
States, it would take the natural resources of two more
Planet Earths.387) First, the society must agree that this is a
necessary objective. Next, some system of incentives to re-
duce and disincentives to use lavishly must be devised.
This is the “carrot–stick” approach. This will involve a cul-
ture change.388 Persons who live in the United States are
constantly bombarded with messages to buy. The advertis-
ing to do this is 500 dollars per person per year. Credit card
companies deluge the average person with offers of cards
that make buying on credit easy. The message is, “Buy
now—Pay later—Why wait to have what you want?” This
makes the objects purchased cost significantly more. One
can think of restrictions on advertising or taxes on adver-
tising and credit cards, but these could be very unpopular.
An approach that has increased the savings rate in some
countries is similar to the Individual Retirement Account
(IRA) used in the United States. Money is set aside before
taxes for purchase of a first home or for a college educa-
tion. There are no taxes until the money is withdrawn for
the intended purpose. Premature withdrawal for another
purpose imposes a tax penalty. (The individual savings rate
in the United States is significantly lower than that in most
other developed nations.)
432
In a finite world, there will be limits to what people can
expect to use.389 This means that the constant growth in the
sales of a product, that some executives seem to expect, is
unrealistic. One can see these unrealistic expectations ex-
pressed in almost any issue of Chemical Engineering
News. The time may come when closed landfills are mined
for the materials in them.
REFERENCES
1. (a) G. M. Levy, ed. Packaging in the Environment. Blackie
Academic and Professional, London, 1993; 150. (b) G.
Matos and L. Wagner, Ann. Rev. Energy Environ., 1998,
23, 107.
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209, 949. (b) R. E. Hughes, G. S. Dreher, M. Rostam-
Abadi, D. M. Moore and P. J. DeMaris, Prepr. Pap.-Am.
Chem. Soc., Div. Fuel Chem., 1996, 41(2), 597; C. A.,
1996, 124, 239, 889.
318. D. NaQuin. Waste Age’s Recycling Time 1997; 9(26):14.
319. J. Beretka, R. Cioffi, L. Santoro, G. L. Valenti. J Chem
Technol Biotechnol 1994; 59:243.
320. G. Parkinson. Chem Eng 1997; 104(5):29.
321. (a) W. Zschau. Int News Fats Oils Relat Mater 1994;
5(12):1375. (b) C. Chung, V. Eidman. Int News Fats Oils
Relat Mater 1997; 8:739.
322. J. H. Krieger, M. Freemantle. Chem Eng News 1997; July
7: 10.
323. W. S. Perkins, W. K. Walsh, I. E. Reed, C. G. Namboodri.
Text Chem Color 1995; 28(1):31.
324. J. D. Underwood. Chem Ind (Lond) 1994; 18.
325. Packag News 1997; May: 6.
326. The Solid Waste Management Problem, 2nd ed. The Coun-
cil on Solid Waste Solutions, 1989; 11.
327. H. Ridgley. Waste Age’s Recycling Times, 1998; 10(7):1.
328. H. Petroski. The Pencil—A History of Design and Circum-
stance, Knopf, New York, 1990.
329. R. L. Maine. Prog Pap Recycl 1993; 2(3):76.
330. D. NaQuin. Waste Age’s Recycling Times 1998; 10(19):3.
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331. Wilmington Delaware Sunday News Journal 1998; Dec
20: B7.
332. M. Billington. Wilmington Delaware News Journal 1999;
Mar 14: B1.
333. Hockessin (Delaware) Community News 1995; Dec 21:
26.
334. P. Gopal. Wilmington Delaware News Journal 1998; Oct
26: B1.
334. G. Gardner. World Watch 1999; 12(4):10.
335. (a) S. E .M. Selke. Packaging and the Environment. Tech-
nomic, Lancaster, PA, 1990; 2nd ed, 1994. (b) E. J. Stil-
well, R. C. Canty, P. W. Kopf, A. M. Montrone. Packag-
ing for the Environment—A Partnership for Progress.
American Management Association, New York, 1991. (c)
G. M. Levy, ed. Packaging in the Environment. Blackie
Academic and Professional, London, 1993.
337. D. Saphire. Benefits of Reusable Shipping Containers—
Delivering the Goods, Inform New York, 1995.
338. The Presidential Green Chemistry Challenge Awards Pro-
gram, U. S. Environmental Protection Agency, Washing-
ton, DC EPA 744-K-96-001, 1996; July: 33.
339. Pollut Equip News 1997; 30(5):4.
340. K. A. O’Connell. Waste Age’s Recycling Times 1997;
9(24):13.
341. K. Holler. Waste Age’s Recycling Times 1997; 9(24):
10.
342. H. Ridgley. Waste Age’s Recycling Times 1997; 9(23):4.
343. Environment 1997; 39(3):23.
344. D. Saphire. Case Reopened—Reassessing Refillable Bot-
tles. Inform, New York, 1994.
345. H. F. French. World Watch 1993; 6(2):32.
346. B. Regan. Am Metal Market Mar 10, 1997; 105(47).
347. S. T. Firkaly. Into the Mouths of Babes—A Natural Food
Nutrition and Feeding Guide for Infants and Toddlers, rev.
ed. Betterway Books, Cincinnati, OH, 1995.
348. (a) V. Komolprasertand, A. R. Lawson. J Agric Food
Chem 1997; 45:444. (b) M. Inagaki, S. Tasaka, M.
Makino. J Appl Polym Sci 1997; 64:1031. (c) N. Inagaki,
S. Tasaka and H. Hiramatsu, J. Appl. Polym. Sci., 1999,
71, 2091. (d) F. Garbassi and E. Occhiello, Macromol.
Symp., 1999, 139, 107. (e) Anon., Mod. Plastics, 2000,
77(1), 12; 2000, 77(6), 12. (f) A. Tullo, Chem. Eng. News,
May 22, 2000, 25.
349. Packag News 1997; May: 6.
350. (a) G. Ondrey. Chem Eng 1999; 106(6):21. (b) M. De-
fosse, Mod. Plastics, 2000, 77(3), 26; 2000 77(8), 23.
351. (a) Letter. G. T. Kimbrough of Ashland Superamerica to
A. S. Matlack, 2/15/96. (b) Packaging 1995; 66(705):13.
352. (a) Chem Eng News 1997; Aug 25: 68. (b) University of
California Berkeley Wellness Lett. 1999; 15(5):8.
353. T. H. Grenby. Pure Appl Chem 1997; 69(4):709.
354. (a) H. Bennett. Chemical Formulary. Chemical Publish-
ing, New York, 1976; 19:308. (b) P. K. Ashurst, Chemistry
and Technology of Soft Drinks and Juices, Sheffield Aca-
demic Press, England, 1998.
355. K. M. Reese. Chem Eng News 1998; June 8: 64.
439
356. H. E. Allen, M. A. Henderson, C. N. Haas. Chemtech
1991; 21(12):738.
357. Anon., Amicus J., 2000, 22(2), 7.
358. Tufts Univ Health Nutr Lett 1997; 15(7):3.
359. Packag Dig 1995; 32(2):68.
360. M. Smith. The U. S. Paper Industry and Sustainable Pro-
duction. MIT Press, Cambridge, MA, 1997.
361. J. Williams. Wilmington Delaware News Journal 1996;
Apr. 25: D1.
362. R. Graff, B. Fishbein. Reducing Office Paper Waste. In-
form, New York, 1991.
363. (a) G. L. Nelson. Chemtech 1995; 25(12):50. (b) R. A.
Denison, Ann. Rev. Energy Environ., 1996, 21, 191.
364. M. B. Hocking. Science 1991; 251:504.
365. Packag Dig 1995; Nov: 42.
366. P. Chatton. Surface Coat Int 1995; 78(11):490.
367. (a) N. Gertler, J. R. Ehrenfeld. Technol Rev 1996;
99(2):48. (b) R. A. Frosch. Environment 1995; 37(10):16.
(c) M. Dwortzan. Technol Rev 1998; 100(9):18. (d) H.
Grann in D. J. Richards, Ed., The Industrial Green Game.
Implications for Environmental Design & Management,
Royal Soc. Chem., Cambridge, 1997, 117–123.
368. M. Nisbet, G. J. Venta, M. Klein. Environ Prog 1998;
17(2):96.
369. H. Kane. World Watch 1997; 10(4):29.
370. (a) C. Hendrickson, L. Lave, F. McMichael. Chemtech
1995; 25(8):56. (b) R. A. Denison, J. F. Ruston, EDF Lett
(Environmental Defense Fund) 1996; 27(5):7. (c) C.
Boerner, K. Chilton, Environment 1994; 36(1):7.
371. (a) World Watch 1995; 8(4):39. (b) K. M. White, C.
Miller. Waste Age’s Recycling Times 1993; Mar 9: 7. (c)
C. Hanisch, Environ. Sci. Technol., 2000, 34, 170A. (d) F.
Ackerman, Why Do We Recycle? Markets, Values & Pub-
lic Policy, Island Press, Washington, D.C., 1997.
372. J. M. Heumann. Waste Age’s Recycling Times 1998;
10:15.
373. Environment 1996; 38(9):22.
374. F. Ackerman. Why Do We Recycle? Markets, Values and
Public Policy. Island Press, Washington, DC, 1997.
375. M. S. Andersen. Environment 1998; 40(4):10.
376. K. A. O’Connell. Waste Age’s Recycling Times 1997;
9(5):1, 9(6):7.
377. F. Ackerman. Environment 1992; 34(5):2.
378. R. F. Stone, A. D. Sagar, N. A. Ashford. Technol Rev
1992; 95(5):48.
379. S. Odendahl. Pulp Paper Can 1994; 95(4):30.
380. Environ Sci Technol 1995; 29(9):407A.
381. D. Saphire. Case Reopened—Reassessing Refillable Bot-
tles, Inform, New York, 1994; 222, 233, 244, 264.
382. K. M. White. Waste Age’s Recycling Times 1997; 9(10):6.
383. (a) Chem Eng News 1997; July 7: 23, (b) P. Layman.
Chem Eng News 1994; Oct 31: 10. (c) L. Gottsching. Pap
Technol 1996; 37(1):47. (d) M. Ryan. World Watch 1994;
7(4):9. (e) M. Ryan. World Watch 1993; 6(5):28. (f) B. K.
Fishbein. Germany, Garbage and the Green Dot: Chal-
lenging the Throwaway Society. Inform, New York, 1994.
440
384. (a) J. M. Heumann. Waste Age’s Recycling Times, 1998;
10(11):29. (b) K. M. White. Waste Age’s Recycling Times
1998; 10(14):4.
385. S. Samdani. Chem Eng 1995; 102(4):21.
386. K. A. O’Connell. Waste Age’s Recycling Times 1997;
9(26):7.
387. E. O. Wilson. Science 1998; 279:2048.
388. (a) G. Gardner, P. Sampat. Mind Over Matter: Recasting
the Role of Materials in Our Lives. Worldwatch
Paper 144, World Watch Institute, Washington, DC, 1998.
(b) J. B. Schor. The Overspent American—Why We Want
What We Don’t Need. Harper Perennial, New York, 1999.
389. (a) D. H. Meadows, D. L. Meadows, J. Randers. Beyond the
Limits. Chelsea Green Publishers, Post Mills, VT, 1992. (b)
A. Durning, How Much Is Enough? The Consumer Society
and the Future of the Earth, Norton, New York, 1992. (c) R.
W. Kates, Environment, 2000, 42(3), 10.
390. An automated plant using similar techniques was sched-
uled to start in Hannover, Germany in 2000. G. Parkinson,
Chem. Eng., 1999, 106(7), 19.
391. J. Garrett, P. A. Lovell, A. J. Shae and R. D. Viney, Macro-
mol. Symp., 2000, 151, 487.
392. S. Strasser, Waste and Want: A Social History of Trash,
Metropolitan Books/Henry Holt, New York, 1999.
393. J. Trittin, Environ. Sci. Technol., 1999, 33, 194A.
RECOMMENDED READING
1. M. S. Turner. Recycling—Information Pamphlet. American
Chemical Society, Washington, DC, 1993.
2. H. Kane. In: L. Starke, ed. Shifting to sustainable industries.
State of the World 1996. Worldwatch Institute, Washington,
DC, 1996; 152–167.
3. J. E. Young, A. Sachs. In: L. Starke, ed. Creating a sustain-
able materials economy. State of the World 1995, World-
watch Institute, Washington, DC, 1995; 76–94.
4. U. S. consumption and the environment. Union of Concerned
Scientists, Cambridge, MA, Feb 1994.
5. P. Harrison. Sharing the blame. Environ Action 1994;
26(2):17; The Third Revolution: Environment, Population
Chapter 14
and A Sustainable World. I. B. Tauris, New York, 1992;
Chap. 18, p. 255.
6. G. L. Nelson. Chemtech 1995; 25(12):50.
EXERCISES
1. Watch your neighbors at home and at school to see
what they discard that is still usable or easily re-
paired. One way to do this is to walk down the street
on trash day before the trash man arrives.
2. Ask a person from an earlier generation what was
used before throwaway items came into common
use. Could we safely revert to these?
3. Check the items in the Good Will or another thrift
store to see what fraction of them are new or practi-
cally new.
4. See what items are sold in bulk in the supermarket.
Figure out how other items might be sold in this
way and thus reduce packaging. Do the same thing
for a hardware store.
5. Look at the ecolabels in a store to see if any might
be misleading.
6. Spun-bonded polyethylene (e.g., Tyvek) is used in
strong mailing envelopes. How should these be
marked so that they would not end up in the recy-
cling of paper, where they cause complications?
7. How could a household waste-exchange program
be set up in your area?
8. The use of computers and e-mail was expected to
reduce the use of paper. Why hasn’t it? Can you de-
vise a system so that these do reduce the amount of
paper that is used?
9. Look at the contents of the trash or recycling con-
tainers next to the photocopiers in your building.
What types of mistakes are people making when
they copy? How would you redesign the photo-
copier to avoid these?
15
Energy and the Environment
I. ENERGY-RELATED PROBLEMS1
Energy is needed for heating, cooling, and lighting homes,
offices, and manufacturing plants; cooking; transportation;
farming; manufacturing of goods; and a variety of other
uses. Homes in the United States use 46% of their energy
for space heating, 15% for heating water, 10% for food
storage, 9% for space cooling, 7% for lighting, and 13% for
other uses.2 The corresponding figures for commercial
buildings are 31, 4, 5, 16, 28, and 16%. Transportation ac-
counts for one-fourth of the energy consumption and two-
thirds of the oil usage in the United States. Industry uses
37% of the energy in the United States. Agriculture, in-
cluding the transportation and processing of foods uses
about 17% of the energy used in the United States. Indus-
trialized societies tend to be energy-intensive. Most of this
energy is derived from fossil fuels. In 1993, oil provided
39% of the world’s energy, natural gas 22%, and coal 26%,
whereas hydropower and other renewable energy sources
provided only 8%.3 Nuclear power accounted for 5% of the
total. This energy consumption has produced various prob-
lems, some of which are quite serious. Even nuclear energy
and renewable energy have problems that need to be
solved. Although technology can solve some of these prob-
lems, others may require changes in our lifestyles, habits,
value systems and outlooks. This review will focus primar-
ily on the role that chemistry can play in solving some of
the problems.4 It will also mention areas in which social
factors play important roles.
A. The Generation of Electric Power460
The burning of coal is used to generate much of the electric
power in the United States. For example, Connectiv (for-
merly Delmarva Power) obtains 40% of its power from
441
coal, 23% from gas, 12% from nuclear, 9% from oil, and
purchases 16% from other sources.5 Strip mining of coal
turns the earth upside down. Although reclamation is now
required, the original diverse natural system is not re-
placed. Instead, a more restricted selection of plants is
used. The soil may be quite acidic owing to oxidation of
iron sulfide (pyrite) brought to the surface during the min-
ing. The same process can result in acid mine drainage into
local steams, resulting a drastic reduction in their biota.
Tailings ponds must be constructed so that no fine coal en-
ters the stream and the dam is strong enough to withstand
heavy rains and possible floods. Mining underground coal
is the most hazardous occupation in the United States. Min-
ers may be exposed to roof falls, dust explosions, methane
explosions, black lung disease from breathing coal dust,
and other problems.
Burning coal in the power plant produces sulfur dioxide,
nitrogen oxides, fine particulate matter, and emissions of
toxic heavy metals, such as mercury (see in Chap. 4). Elec-
tric power generators are responsible for 66% of the sulfur
dioxide, 29% of the nitrogen oxides, 21% of the airborne
mercury, and 36% of the carbon dioxide released in the
United States.6 Many old plants in existence when the
Clean Air Act was passed were exempted from the regula-
tions. It has been estimated that if the 559 dirtiest plants
met the current source emissions standards, this would cut
the emission of nitrogen oxides by 69% and that of sulfur
dioxide by 77%.7 Although emissions of sulfur dioxide,
carbon monoxide, and lead have fallen since 1988, ground-
level ozone has remained about the same, and nitrogen ox-
ides are increasing.8 Annual crop damage from ground
level ozone in the United States is about 3 billion dollars.9
The sulfur dioxide comes from sulfur in the coal. Al-
though inorganic sulfur in pyrite can be removed by flota-
tion of fine coal, organically bound sulfur is much harder to
442
remove, and usually is not. The sulfur dioxide in stack gas
is often captured with lime to form calcium sulfite, which
can be oxidized to calcium sulfate (gypsum). In places such
as Denmark and Japan, this gypsum is used in making wall-
board for houses. In the United States only 5% of this gyp-
sum is used in wallboard because it cannot compete with
natural gypsum.10 The result is that more than 12 million
tons of flue gas gypsum is landfilled each year in the United
States. Ways of removing the sulfur dioxide with regener-
able adsorbents have been studied, but do not seem to be in
widespread use.11
Nitrogen oxides are produced when fuels are burned at
high temperatures. The amount formed is less at lower tem-
peratures. Catalytic combustion using a palladium catalyst
has been studied as a way to burn the fuel at a lower tem-
perature.12 Nitrogen oxides can also be removed by reduc-
tion of the stack gases with ammonia, hydrogen, carbon
monoxide, or alkanes using various catalysts to form nitro-
gen.13 Nitrogen oxides formed during combustion react
with hydrocarbons in the presence of light to form ground
level ozone. The U. S. Environmental Protection Agency
(EPA) has proposed to require deep cuts (up to 85%) in the
amount of nitrogen oxides emitted by power plants in the
eastern United States as a way to reduce ground level
ozone.14 This may require more than just burning at a lower
temperature. The Edison Electric Institute, a trade associa-
tion of utilities, calls the proposal “unfair, expensive and
misdirected.” The American Chemistry Council (formerly
the Chemical Manufacturers Association) is also concerned
about the proposal. Motor vehicles produce about half of
the nitrogen oxides in the air. Power plants produce most of
the rest. Ships at sea account for 14% of the total emissions
of nitrogen oxides, from the burning of fossil fuels, and
16% of the sulfur dioxide arising the burning of petroleum.
Their residual oil fuel may contain as much as 4.5% sul-
fur.15 Some of these emissions drift over and fall out on
land in places such as Scandinavia. Acid rain from sulfur
dioxide and nitrogen oxides emissions16 has wiped out the
fish populations in 9500 lakes in Norway with another 5300
remaining at risk.17 Much of the emissions arise in other
countries, such as the United Kingdom and drift in with the
winds.18 (A study by the British government concluded that
up to 24,000 persons die prematurely in the United King-
dom each year following short-term air pollution episodes
involving ozone, particulates, and sulfur dioxide.19) Simply
reducing the supply of acid rain now may not be enough to
restore these lakes, because the buffer capacity of the soil of
the watershed may have been exhausted. Such depletion of
calcium ions in the soil has been documented in the moun-
tains of New Hampshire in the United States.20 Acid rain
also causes reductions in crop and timber yields, as well as
corrosion of metals in cars, power lines, and such, and of
Chapter 15
buildings made of limestone, marble, and sandstone. It is
also partially responsible for the eutrophication of water in
places such as Chesapeake Bay in Maryland.
Power plants are also among the sources of the fine par-
ticulates (under 2.5  m) that are beginning to be regulated
by the U. S. Environmental Protection Agency as a way to
better health. Better electrostatic precipitators or scrubbing
devices may be needed to control these. (Other sources in-
clude motor vehicles and the burning of wood. In Los An-
geles, 14% of the fine carbon-containing particles come
from residential fireplaces, with the value going up to 30%
in winter.21) This, together with lowering the ozone stan-
dard from 0.12 to 0.08 ppm is expected to prevent 15,000
premature deaths and up to 350,000 cases of aggravated
asthma each year in the United States.22 These new stan-
dards are unpopular with American industry.23
The fly ash formed in coal combustion also represents a
disposal problem (see also Chap. 14). Although there are
some uses such as in concrete and bricks, soil stabilization,
soil conditioner, and landfill cover, more need to be
found.24 Additional uses in wallboard, concrete blocks, and
other construction materials should be possible. Other
ashes include bottom ash and boiler slag. Experiments have
been run on the recovery of iron, aluminum, and other met-
als from the ashes, but the processes may not be economi-
cal at this time. This could reduce the need to mine for these
other materials. Coal-fired power plants produce over 100
million tons of ash annually in the United States. Coal fly
ash is routinely mixed with water and put into settling
basins. This process extracts some arsenic, cadmium, mer-
cury, selenium, and strontium into water, which can then
cause abnormalities in amphibians.25
About 34% of the energy in the coal is recovered as
electricity in the usual power plant.26 The rest goes out in
the cooling water. Water drawn in from a river or lake con-
tains fish, fish larvae, fish eggs, and a variety of other or-
ganisms that are often killed in the process. Fish screens
have been designed to divert fish, but do nothing for
smaller organisms. These are killed when the cooling wa-
ter is chlorinated to prevent biofouling of the tubes. The
exit water must then be dechlorinated by reducing the chlo-
rine to chloride ion with sulfur dioxide, sodium sulfite, or
sodium metabisulfite to avoid killing more organisms in
the receiving body of water.27 The thermal pollution from
the released water can help fish and shellfish grow more in
the winter, but can be deadly to them in the summer. Sub-
stitution of cooling towers for the once-through cooling
water would reduce the losses of organisms, but would be
more expensive.28 Air cooling is also possible but may be
even more expensive. There is an urgent need to find uses
for this waste heat. One of the best ways is to use it to heat
and cool buildings in a process called district heating. (The
Energy and the Environment
waste heat can also be recovered as steam for industrial
plant use, the process being called cogeneration.) This can
recover 80–85% or more of the energy in the fuel29 and is
often used in Europe. (The waste heat from the power plant
just north of Wilmington, Delaware, could be used for this
purpose in buildings in downtown Wilmington, but it is
not.) Perhaps, further research on cheap, efficient insula-
tion for the pipes is needed. Drag-reducing surfactants,
such as N-cetylsarcosinate (C16H33N(CH3)CH2CONa)
can reduce drag in these systems as much as 70%.30 More
research is needed on methods of transforming this waste
heat to a stored form that can be shipped as a liquid or in a
slurry in a pipe for reclaiming at more distant locations.
(Heat storage systems are discussed later.)
B. Transportation
The 5% of the world’s population living in the United
States consumes 26% of its oil.31 The transportation sector
uses 65% of this oil. Almost all (97%) transportation in the
United States relies on oil. Personal automobiles consume
50% of the oil.32 Gasoline consumption was almost 114
billion gal in 1996.33 America’s drivers burned an average
of 336 million gal of gasoline per day for the first 8 months
of 199734. Half of this oil was imported. In June 1992, the
cost of this oil plus the importation of cars in which to use
it was 6.6 billion dollars.35 Partly as a result of this, the
United States is now the world’s largest debtor nation.36
Europe imports 76% of its petroleum.37 Transportation
produces 20% of all carbon dioxide in the world and 67%
of the pollutant emissions in the world’s cities.
Numerous environmental problems are associated with
the production and use of this oil. Oil spills were discussed
in Chap. 1. Extensive studies have been made of the fate of
the oil spilled in Alaskan waters from the Exxon Valdez.38
Leaks in pipelines have also been problems.39 Twenty-five
15.1
443
years after a spill in Alberta, Canada, large amounts of oil
were still present at depths of 10–40 cm. Motorists who
change their own oil often dump the used oil down a storm
drain, from which it finds its way to the nearest river. Ef-
forts to eliminate this practice include laws, providing con-
venient collection stations for used oil, and painting warn-
ing signs on the pavement next to storm drains. Oil can also
get into water from the exhausts of older outboard motors
which burn a mixture of 1 qt of oil to 1 gal of gasoline.
There is also the problem of what to do with used drilling
muds and oil well brines, especially on offshore drilling
platforms. The methyl tert-butyl ether added to gasoline to
reduce air pollution is now showing up in shallow wells
and springs in several urban areas.40 This could result both
from spills and by evaporation or leakage from tanks. Most
of it in Donner Lake, California, comes from recreational
boating.41 The current requirement for its use is being de-
bated, and the additive is being phased out.42 Substitution
of ethanol for it could accomplish the same goal without
the pollution.
Motor vehicles are responsible for much of the ground
level ozone. They produce half of the nitrogen oxides in the
air. Heavy-duty diesel engines account for a quarter of
this.43 There are about 5 million heavy-duty diesel engines
and 2 million light-duty diesel engines on roads in the
United States. Short (50 nanosecond) electrical bursts can
eliminate not only the nitrogen oxides, but also the soot in
the diesel exhaust. In addition, motor vehicles emit un-
burned hydrocarbons and carbon monoxide. The cost of air
pollution caused by cars and trucks in the United States has
been estimated at $30–$200 billion/yr.44
The soot from diesel engines and wood smoke carry mu-
tagenic polycyclic aromatic hydrocarbons and their nitro
derivatives.45 Some typical ones are shown in 15.1, the first
being a potent mutagen in the Ames Salmonella test. Cat-
alytic afterburners (containing platinum) are now required
444
on new wood stoves sold in parts of the United States to re-
duce air pollution from them.
Motor vehicle transport accounts for half of the world’s
oil consumption and generates one-fifth of all greenhouse
emissions. Tailpipe emissions are the largest source of air
pollution in nearly half of the cities of the world, surpass-
ing wood fires, coal-burning plants, and chemical manu-
facturing.46 New rules for lowering the maximum sulfur
content in gasoline and diesel fuel, both in the United
States47 and in Europe,48 are designed to reduce this pollu-
tion by enhancing the performance of catalytic converters.
(The average sulfur content in U.S. gasoline in February
1999 was 330 ppm.) A new method for removing diben-
zothiophenes from petroleum has been demonstrated in the
laboratory.49 A mixture of light oil and acetonitrile con-
taining 9, 10-dicyanoanthracene was irradiated with visible
light in air to oxidize the sulfur compounds. The products
remained in the acetonitrile layer. (See Chap 9 for biologi-
cal removal of sulfur from petroleum.)
Urban sprawl is a big part of the problem in the United
States. Americans in cities drive five times as far as persons
who live in European cities.50 The United States has more
cars per capita than any other developed nation.51 An Aus-
tralian has described the situation as “totally out of con-
trol.” Only 3% of travel in U.S. cities is by public transport.
One-fourth of the travel in European cities is by this
method, whereas in Hong Kong and Tokyo two-thirds is.
Close to half of all urban space in the United States is for
cars. The average time to commute to work in the United
States is 22 min.52 Only 5% travel to work by public trans-
portation. Only 4% walk to work. Only 22% of car miles
are to work, whereas about a third are to pick up children
and to go shopping.53 Many children are effectively immo-
bilized by unsafe roads and the lack of sidewalks in subur-
bia which prevent them from walking. Children old enough
to drive cars often go to shopping malls to find a place to
walk and meet their friends. Some of them also have a cu-
rious energy-intensive pasttime of cruising their cars round
and round a loop in the center of Newark, Delaware, on Fri-
day night, as they watch their friends in other cars. Widen-
ing roads accounts for 44% of highway costs. Subsidies to
roads are seven times those for public transportation. The
difference between work and welfare in the inner city may
be whether or not there is adequate public transportation.
The problem in the United States is becoming worse.
The population in Delaware grew 11% in the last 10 years,
but the number of vehicle miles went up 55%.54 There is
now 0.91 car per licensed driver.55 Delaware cars average
17 miles/gal. The problem is that the price of gasoline is too
low. At $1.17/gal, it is cheaper in inflation-adjusted dollars
than it was in 1960.56 At $1.10/gal, it is the cheapest in in-
flation-adjusted dollars that it has ever been in the 79-year
Chapter 15
history of recorded pump prices.57 It is cheaper than milk,
apple juice, and even, some mineral water. Americans are
choosing less fuel-efficient cars today. Sport utility vehi-
cles, vans, and light trucks, which are not subject to gov-
ernment fuel efficiency standards,58 are now almost half of
the total fleet. Americans tend to choose larger cars over
smaller ones59 for safety. They also choose options that
lower mileage, such as the ability to accelerate rapidly,
four-wheel drive, antiskid brakes, automatic transmission,
air conditioning, and such. Advertisement for new cars
emphasize more power, more pickup, more ability to drive
off the road, and more luxury.60 The raising of speed limits
above 55 mph has not helped, because fuel efficiency de-
clines above this speed.
The cost of mobility in the United States is about 20%
of the family income. In Europe, the figure is closer to 7%.
The problem is that much of the cost of automobile trans-
portation is hidden. For each dollar that the average Amer-
ican associates with his car, there is a 2 dollar hidden sub-
sidy in the form of road construction and repairs, street
maintenance, traffic management, and parking enforce-
ment. It has even been suggested that the price of the Per-
sian Gulf War be paid for at the gas pump. Taxes on gaso-
line are relatively low in the United States, but are 64% in
the European Union.61 Suggestions for putting the cost
where the motorist can see it include road-use taxes, elim-
ination of free parking except in very small lots, linking the
cost of car insurance and license fees to the miles traveled,
elimination of free company cars, taxes on gas guzzlers,
and such. Taxes and subsidies might be rearranged so that
it is expensive and inconvenient to drive one person per car,
but inexpensive and convenient to take public transporta-
tion or to walk or bike. A double-track rail line can carry as
many passengers as a 16-lane highway. A subway uses
one-sixth as much energy per passenger as a car carrying
one person. Air travel is more energy-intensive than travel
by rail, suggesting that trips of 100–200 miles should be
made by rail. Supersonic aircraft62 require twice as much
fuel per passenger mile as regular aircraft.
Alternatives to sprawl include clustered housing and
public transit-oriented development.63 A return to more
compact living with village-like living has been pro-
posed.64 People in compact neighborhoods in San Fran-
cisco made 42% fewer trips by car than suburbanites.65
Mixed use developments cut auto use. Portland, Oregon,
has urban growth boundaries and other laws that are lead-
ing to a more livable city.66 Curitiba, Brazil, has an inte-
grated public transportation system that functions well.
The combination of cheap gasoline, few safe places to
walk in suburbia, and abundant food has made one-third
of Americans obese (i.e., 20% or more over optimum
weight). World oil production is predicted to peak in
Energy and the Environment
2010.67 (U.S. oil production peaked in 1970.) To moder-
ate the problems associated with global warming, it would
be desirable to change to a less energy-intensive system
long before 2010.
C. Miscellaneous Problems
There has been a tendency to mechanize all sorts of tools
and gadgets in the name of saving labor or living a life of
luxury. Gasoline-powered lawn mowers and chain saws
emit just as much pollution as the outboard motors men-
tioned in the foregoing.68 This is many times what comes
out of the tailpipe of an automobile for the same amount of
fuel consumed. Lawn mowers and saws that are run by
hand are still available, although not very common. They
give the operator more exercise. There is some question as
to whether the average home owner needs a powered tooth
brush, pencil sharpener, carving knife, can opener, lawn
edger, or leaf blower. Some of the larger items may even be
purchased as status symbols.
Single-use throwaway items require more energy to
make than reusable ones on a per use basis, as discussed in
Chap. 14. The production of ammonia for fertilizers is en-
ergy-intensive. Much of it could be replaced by legumi-
nous cover crops, less lawn, as mentioned in Chap. 11.
Run-off of excess fertilizer has caused a dead zone of 6000
15.2
445
miles2 to form in the Gulf of Mexico.69 It has also led to
Pfiesteria-caused fish kills in North Carolina and Mary-
land.70
Ammonia manufacture from nitrogen and hydrogen is
an energy-intensive process that consumes about 5% of the
world’s production of natural gas (for fuel and as a source
of hydrogen).71 The reaction is usually run at about 450°C
over an iron catalyst at about 10% conversion per pass.
Chemists have long-sought a milder, better way to do this.
Recent research suggests that such a route may be possible.
Molybdenum amides have been used to split nitrogen to
form molybdenum nitrides (15.2).72 Hydrogen alone does
not reduce this to ammonia, but catalysts that intermedi-
ately form metal hydrides might. These include catalysts
containing iron, nickel, cobalt, palladium, platinum, and
such. A manganese nitride has been used as a source of am-
monia in a reaction with a double bond (15.2).73 The chal-
lenge is to figure out the mechanism of this reaction so that
modifications can lead to the preparation of ammonia in the
form of more useful compounds.
Other experiments on nitrogen fixation have used tran-
sition metal complexes of nitrogen.74 One used a tungsten
nitrogen complex with a ruthenium hydrogen complex at
55°C to produce a 55% yield (based on tungsten) of am-
monia.75 Intermetallic compounds of iron and titanium
have been used with ruthenium on alumina to make some
446
15.3
ammonia, at 450–500°C, via interstitial metal nitrides.76 In
another example, a titanium–nitrogen complex formed in
situ was converted to a trimethylsilylamide which was then
used to convert benzoyl chloride to benzamide (15.3) in
88% yield.77
Although these leads are suggestive, considerable addi-
tional work may be needed to devise a practical commer-
cial system of making ammonia.
The use of nuclear energy to generate power produces
no greenhouse gases, but it can cause pollution.78 Mining
the ore exposes the miners to radon, which can cause can-
cer. In one area in Colorado, houses were built on radioac-
tive tailings piles. Nuclear plants, such as the one in Salem,
New Jersey, require massive amounts of cooling water.
The use of cooling towers reduces this. Even if, in normal
operations, negligible amounts of radioactive materials are
emitted, there is the possibility of accidents, as seen at
Chernobyl and Three Mile Island, as described in Chap. 1.
Accidents of this type can expose many more people over
a much larger area than an accident in an ordinary chemi-
cal or power plant. There is also the unresolved problem of
long-term storage of the used fuel. An underground repos-
itory for nuclear weapons-related waste opened near Carls-
bad, New Mexico, in 1999.79
The cost of electricity produced in this way is higher
than that produced from conventional fuels. France pro-
duces 75% of its electricity in nuclear plants, Sweden 51%,
Switzerland 42%, Spain 38%, Japan 28%, Germany 27%,
and the United States 22%. There are 100 nuclear power
plants in the United States.80 Sweden has voted to phase
out nuclear energy. The German government wants to
phase out the nuclear power industry.81
Environmental problems can also be present when re-
newable sources of energy are used. Condensed steam
from geothermal plants may have to be cleaned up before it
can be discharged. Reinjection into the reservoir avoids
this problems. Hydropower requires dams that remove the
niches in running streams that foster biodiversity. Cool,
well-aerated running water favors different species more
than lakes do. A shaded stream can have a different flora
and fauna that may be more diverse than that in the sunny
lake behind the dam. The dams also interfere with the
Chapter 15
spawning of migratory fishes, such as salmon, shad, and
eel. Further research on fish ladders is needed to develop
more effective designs.
The use of biomass for energy can also involve problems.
Half of the wood harvested in the world is used for fuel for
heating and cooking. In many developing nations, this is re-
sulting in increasingly long trips for wood and in deforesta-
tion. If other ways can be found to provide the needed en-
ergy (e.g., by tapping the sun’s energy), reforestation may be
easier to accomplish. A biomass-to-energy plant on the Big
Island of Hawaii destroyed about half of the remaining pri-
mary forest before it was closed. (Hawaii has a very high in-
cidence of endemic plants that evolved because of its isola-
tion.) Harvesting of peat for fuel in northern Europe is
threatening the bog flora. The harvesting of whales for oil
for lamps in the 19th century may have started their decline.
Very high particulate levels results from cooking on un-
vented biomass stoves in rural Mexico.82 Typically, tortilla
cooking is done 3–4 days a week, with 2–4 h each day. The
use of liquified petroleum gas eliminates the particulates,
but produces another problem in cities. In Mexico City,
leaks of this gas accounted for one-third to one-half of the
hydrocarbons in the air.83 (Mexico City is notorious for its
severe air pollution. Ozone levels often reach 0.20–0.30
ppm.) Traditional tortilla making uses a lot of water and en-
ergy and results in a discharge of water containing a lot of
lime. A careful study of this process has reduced the waste
greatly by using exact amounts of lime and water together
with infrared cooking in a cheaper process.84
D. Global Warming85
The world is now 0.7°C warmer than it was in the 19th
century, according to the United Nations Intergovernmen-
tal Panel on Climate Change.86 Eleven of the past 16 years
have been the hottest of this century. 1998 was the warmest
year up until that time since record keeping began in 1856.
Based on tree rings, pollen, sediments, gases trapped in
glaciers, and corals, it was the hottest year in the last 1000
years.87 This is the greatest rate of temperature change in
the last 10,000 years. Global minimum temperatures are
rising faster than the maxima.88 Temperatures in polar re-
Energy and the Environment 447

gions have risen faster than the global average (e.g., as migrate poleward, a process that may be difficult consider-
much as 6°C in Alaska). ing the extensive habitat fragmentation in many countries.
Although the presence of aerosols from volcanoes and The responses to global warming can be seen in some
air pollution have complicated the study,89 it is now be- species already. A gradual warming of the California cur-
lieved to be due to human’s activities. It is due to putting rent by 1.2–1.6°C since the 1950s has resulted in a 80% de-
more greenhouse gases, such as carbon dioxide, nitrous ox- cline in the zooplankton, a 60% decline in Cassin’s auklet,
ide, chlorofluorocarbons, hydrofluorocarbons, perfluoro- and a 90% decline in the sooty shearwater.99 More winters
carbons, and sulfur hexafluoride, into the atmosphere.90 without sea ice in Antarctica have caused a drop in the krill
Sulfur hexafluoride is the most potent, being 23,900 times population.100 Birds are laying their eggs earlier in the sea-
as potent as carbon dioxide.91 Efforts are being made to re- son in the United Kingdom.101 The bleaching of corals on
duce its use by the electrical and other industries, or at least tropical reefs is considered by some to be an early warning
to use systems to capture it for recycling. Carbon dioxide is sign of global warming.102 The range of Edith’s check-
by far the largest, amounting to 23 billion tons each year.92 erspot butterfly in the western United States, Mexico, and
The preindustrial level of 280 ppm in the air has risen to Canada is moving northward.103 There is also the fear that
356 ppm today, largely from the burning of fossil fuels.93 global warming could shift ocean currents, with the result
This value could reach 500 ppm by the year 2100 and re- that Europe could become much colder.104
sult in a rise of global temperature of 1.0–3.5°C. This Agriculture may expand northward, but crop yields in
warming was first predicted by Arrhenius 100 years ago.94 existing agricultural areas could suffer if they become
The United States with 5% of the world’s people pro- drier. Growers promote faster growth of some greenhouse
duces about one-fourth of the carbon dioxide emitted each crops by adding carbon dioxide, but the effect is not gen-
year, the most of any developed nation (Table 15.1). eral. Photosynthesis may rise in C3 plants, with less rise in
In 1990, the biggest producers of carbon dioxide after C4 plants.105 If carbon dioxide is not the limiting nutrient,
the United States were the former Soviet Union, China, and no increase in growth may occur. The amount of detrital
India.95 China was the second largest emitter after the carbon is three times that held in living plants.106 Elevated
United States in 1996.96 Brazil also contributes a lot owing carbon dioxide levels on some plants can result in changes
to land clearing. in the soil fungi and the arthropods that feed on them.107 A
Along with the increase in temperature by 2100 will rise in temperature may cause more rapid decomposition of
come a rise in sea level of 15–95 cm.97 Glaciers and islands carbon in the soil by bacteria and fungi, with the result that
will shrink. More frequent extreme weather events such as the total system becomes a net emitter of carbon dioxide,
droughts and floods are expected. A 1-m rise in sea level rather than a sink. Arctic tundra is now a source of carbon
would threaten half of Japan’s industrial areas. An esti- emissions, rather than a sink.108
mated 118 million people may be at risk from the rising sea Warmer temperatures may cause vectors for tropical
level.98 Many species of plants and animals will have to diseases to move northward.109 These include malaria,
schistosomiasis, dengue fever, cholera, and others. Malaria
and dengue fever are already occurring at higher altitudes
Table 15.1 Carbon Dioxide Emissions by Country
than they used to. More heat waves will mean more heat-
Nation CO2 emitted in millions of metric tons related deaths, as happened recently in Chicago.
Various suggestions have been made for sequestering
United States 4,957 some of the carbon dioxide. Planting trees (e.g., on de-
Japan 1,173
graded land), could remove 12–15% of fossil fuel emis-
Germany 1,012
United Kingdom 584
sions during 1995–2050.110 Tropical forests can sequester
Canada 457 up to 200 metric tons of carbon dioxide per hectare. Or-
Australia 289 ganic farming with cover crops, can put more carbon back
Spain 261 into the soil (see Chap. 11). Carbon dioxide can be made
Netherlands 168 into useful products by chemical reactions.111 One reaction
Czech Republic 170 is the treatment of carbon dioxide with hydrogen to pro-
Austria 59 duce methanol or dimethyl ether for use as fuels.112 The hy-
Sweden 61 drogen must be obtained from renewable sources (e.g.,
Denmark 52 electrolysis of water using electricity from hydropower,
Switzerland 44 wind energy, or solar energy). If it is made in the usual way
Norway 36
by reaction of methane with water, there is nothing to be
New Zealand 2
gained. Since much more petroleum and natural gas are
448
used for fuels than for the production of chemicals, the sig-
nificant reduction of carbon dioxide levels by this method
would require a major expansion of the chemical industry.
Because the chemical industry consumes 22% of the en-
ergy used by American industry, it needs to reduce emis-
sions of carbon dioxide.113 The production of cement gen-
erates 10% of the carbon dioxide produced by humans.114
The worldwide use of energy for refineries is 5 million bar-
rels of oil per day.
Other suggestions are to put the carbon dioxide into
saline aquifers at least 800-m (2600-ft) deep or into the
ocean below 3500-m (11,500 ft).115 Although this may be
a way of handling some of it, there are some unanswered
questions. Deep-well injection of chemicals has had some
undesirable side effects and is being curtailed. Some artifi-
cial earthquakes have been produced this way. A natural
earthquake that released the gas suddenly could kill people
in the vicinity, just as the carbon dioxide released by an
overturning lake did in the Cameroon. It would also be dif-
ficult to collect the carbon dioxide from mobile sources,
such as cars and trucks. However, if they were all electric,
the carbon dioxide could be collected at a central power
plant. In addition, the large amounts of carbon dioxide
emitted would require a large number of injection wells.
The hydrates that form when liquid carbon dioxide is put
into the deep ocean spread out in pools on the ocean floor,
then dissolve in water that would be moved by ocean cur-
rents.116 It seems much better to reduce our consumption
through increased energy efficiency and to switch to re-
newable sources of energy.117
The extent of concern about global climate change
varies. Insurance companies are concerned because more
storms in recent years have caused them to pay out more
money than expected to settle claims.118 Low-lying island
nations are concerned, for they stand to lose more with ris-
ing sea levels. The Union of Concerned Scientists issued a
statement endorsed by 1500 prominent scientists, including
98 Nobel Prize winners and dozens of officials of national
academies, calling for definite action to reduce emissions
to below 1990 levels.119 The Kyoto Treaty of 1997 calls for
nations to reduce their greenhouse emissions,120 but some
observers feel that the reductions agreed on will not be
nearly enough to stabilize the world climate.121 There is
also much bickering among nations over which should do
how much and in what way.122
Companies and countries that profit from the sale of oil
seem less concerned.123 The head of Exxon says:
A number of countries, including the United
States, appear to be on a policy course that could
cause steep reductions in the consumption of oil and
other fossil fuels, on the unproven theory that their
Chapter 15
use significantly affects Earth’s climate. Such a pol-
icy could have a severe economic impact and force
drastic changes in lifestyles and standards of living
all over the world.124
The Global Climate Coalition, the U.S. fossil fuel sec-
tor’s lobbying arm, says: “It’s really not necessary to begin
reducing emissions by 2005.”125 British Petroleum, which
has a division that makes solar cells, feels that the time to
begin to reduce emissions is now.126 Shell, General Mo-
tors, Monsanto, Sunoco, and duPont feel that it is time to
begin reducing emissions, but the American Chemistry
Council (formerly the Chemical Manufacturers Associa-
tion) is opposed to taking the actions required by the Kyoto
agreement.127
Estimates of the cost to prevent further global warming
vary widely.128 A United Nations report on global warming
says that the effects of global warming could be mitigated at
surprisingly little cost.129 A study by the Pew Center on
Global Climate Change concluded that emissions in devel-
oping nations can be reduced without slowing down the
countries’ economic growth.130 A group of 2400 scientists
feel that the total benefits from reducing emissions will out-
weigh the cost.131 They feel that the change can be made
without harming employment or living standards. The cost
of reducing emissions using some of the advanced technolo-
gies now available or on the horizon will be virtually zero,
according to two workers in the field.132 The U. S. Depart-
ment of Energy calculates the net economic cost to stabilize
emissions is near zero.133 The World Resources Institute has
estimated that stabilizing carbon dioxide emissions at 1990
levels by 2020 will have a minimal effect on the U. S. econ-
omy.134 The costs of the new technologies will be offset by
savings in the fuel that will not have to be purchased.
On the other hand, the “Global Climate Coalition,” a
lobbying group for the fossil fuel industry, concludes that
stabilizing emissions would cost each household $2061
each year. Charles River Associates estimates the cost of
complying with the Kyoto protocol at $100 billion/yr.135
The Argonne National Laboratory says that limiting emis-
sions could devastate energy-intensive industries, such as
the chemical industry and cost many jobs.136 Critics of this
study say that it is not possible to approach the problem by
a single-sector way. Jobs lost in the oil industry might be
replaced by new ones in the photovoltaic cell industry.
Dale Jorgenson, an economics professor at Harvard Uni-
versity, feels that trying to stabilize greenhouse gases in the
atmosphere “would be very, very damaging to the world
economy.”137
Because 5% of global carbon emissions come from U.S.
transportation (more than any other sector in in other coun-
try), this is a good place to start reductions.138 Improved
Energy and the Environment
fuel efficiency standards for American motor vehicles have
been suggested as one way to reduce emissions. However,
a group called the Coalition for Vehicle Choice opposes
such standards.139 Hybrid vehicles with electric motors and
gasoline or diesel engines that will have twice the fuel effi-
ciency of currents cars are under development.140 Carbon
taxes, which have been proposed as a way to limit emis-
sions, are very unpopular with the chemical industry.141 It
should also be possible to eliminate the 58 billion dollars of
annual subsidies in the world for fossil fuels.142 One can
conclude from the general foregoing discussion that, when
major changes are required, a lot of politics can be in-
volved. The success of the Montreal treaty in protecting the
ozone layer suggests that it should be possible to use a sim-
ilar treaty (the Kyoto treaty or some modified version) for
global warming.143 There should also be new business op-
portunities for those who are willing to go into new ar-
eas.144 Unfortunately, the research and development activ-
ity of the U. S. energy sector in 1999 was extremely low.145
II. HEATING, COOLING, AND LIGHTING
BUILDINGS
A. Use of Trees and Light Surfaces
The large savings in energy that can result from living
closer to work in more compact cities146 was discussed ear-
lier. The saving of energy by using waste heat from the
generation of electricity for heating and cooling of build-
ings was also mentioned. Cities are islands of heat not only
due to the artificial lighting used in buildings, but also due
to the many black surfaces that absorb heat from the sun.147
One-sixth of the electricity used in the United States is used
to cool buildings. A combination of lighter roofs, walls,
and road surfaces, together with the planting of shade trees
in appropriate places can reduce the need for air-condition-
ing by 18–30%.148 (The range on houses may be as much
as 10–70% depending on factors such as the amount of in-
sulation in the attic and others.) It could make Los Angeles
5°F cooler in the summer. A black roof reflects 5% of so-
lar energy, whereas a white roof reflects 85%. As a white
roof becomes dirty, its effectiveness can be reduced by
20%.149 Washing with soap and water returns its maximum
effectiveness. A self-cleansing roof surface might be made
with a surface layer of titanium dioxide catalyst for light-
catalyzed destruction of the dirt150 (see Chap. 8). Another
alternative is a surface of a perfluorinated polymer to which
the dirt would not adhere well, so that rain could wash it
off. Concrete roads absorb less heat from the sun than ones
of black asphalt. Parking lots can be shaded by trees in traf-
fic islands. For individual homes, deciduous trees can be
planted on the west and south sides to cast maximum shad-
449
ows on the house. A tree on the east can be used to shade
the air-conditioner. Shrubs around the foundation will re-
duce the temperature of the walls and the adjacent soil.
Coniferous trees can be planted on the north side to break
winter winds.
B. Solar Heating and Cooling
Passive solar heating and cooling151 can save 50% of the
energy needed for a home at the latitude of Philadelphia,
Pennsylvania. (A building in temperate, semiarid Ar-
gentina that used this technique saved 80% of its heating
costs.152) This involves putting the long face of the build-
ing toward the south. Living spaces can be put on the south
and storage spaces and garages on the north. Large win-
dows are put on the south side and small on the north. Other
windows are located to allow cross-ventilation in the sum-
mer. Overhanging eaves are set to keep out the summer
sun, but to allow the lower winter sun to enter the building.
The windows should be double or triple glazed with ther-
mal breaks, (i.e., insulation), on any metal frames. The
building must be well-insulated and weather-stripped. A
large mass of concrete, brick, or stone is put in a floor, in-
terior wall, or chimney to store heat overnight. A vent on
the roof can be arranged so that heat rising in a stack effect
can be used to bring cooler air into the building in the sum-
mer. Small turbines used in this way are driven by the ris-
ing air or by the wind. Ventilation at night will cool down
the building, which, if closed in the morning, will take quite
a while to warm up. Heat exchangers can be used with ex-
haust air to recover some of its heat during the winter.
Additional possibilities include putting a solar water
heater on the roof and drying the laundry on a line outside,
instead of in a clothes dryer. Heat pumps can be used to up-
grade low-grade heat, such as that found in used cooling wa-
ter and wastewater.153 A heat pump that draws its heat from
the ground, rather than the air, will be more efficient in cool
weather.154 A water loop geothermal heat pump that circu-
lated water around a building’s hot and cool sides and that
replaced a boiler saved 54% of the energy under optimum
conditions.155 An electric utility company in Delaware sug-
gests vertical loops 10 to 15-ft apart that go to a depth of
80–180 ft.156 (The temperature of the ground below about
30 ft is constant the year round in Delaware.) A groundwa-
ter system heat pump in Portland, Oregon, is still good after
50 years of operation.157 Air drawn in through underground
pipes can be used for cooling in the summer and is partially
preheated for use in winter. Before the large-scale adoption
of air-conditioning, some Chicago hotels were cooled by air
drawn in from the city’s system of tunnels. A cinema in In-
dia has been cooled by a combination of evaporative cool-
ing, a wind tower, and an earth air tunnel.158 There is a pos-
450
sibility of locating a refrigerator in the home such that it
could be cooled in part by outside winter air. Buildings can
be heated by putting a transparent plate in front of a wall,
preferably blackened, with an air gap in between.159 The air
that heats up in the gap can be moved into the building with
a small fan. Such a method can be used to retrofit existing
buildings. Solar heat pipe panels have also been used to
transfer heat from outside to the inside of the building.160
The water left in the evacuated tube evaporates on the hot
outside end and condenses on the cooler end on the inside of
the building. Solar roofs have been used to heat air in North-
ern Ireland.161 Solar energy has also been used for district
heating with the aid of parabolic concentrators that focus the
sun’s rays on a pipe containing water.162
Efforts have been made to optimize the absorption of
heat by the black surface. One paint consists of a mixed ox-
ide of iron, manganese, and copper with phenoxy and sili-
cone resins.163 Stainless steel–aluminum nitride coatings,
made by magnetron sputtering, have a solar absorptance of
0.93–0.96.164 Alumina pigmented with nickel particles is
in common use in solar collectors. It has a solar absorp-
tance of 0.96 and a thermal emittance of 0.12–0.17 at
60–100°C.165 A black chrome consisting of CuCrO4 
CuO  Cu2O absorbed more than 0.9 units in the visible
with less than 0.1 thermal emittance in the infrared.166
Black nickel is said to be as good as black chrome.167 To
maximize the absorption of heat, one system uses a U-
shaped apparatus with a porous matrix in the back channel
(Fig. 15.1).168 Another uses a transparent honeycomb insu-
lation in the top and bottom covers.169
A new solar cooker uses an aluminized plastic sheet
parabolic reflector to direct the sun’s heat to a storage block
Figure 15.1 Counterflow solar air heater with porous matrix.
Reprinted from Sol. Energy, vol. 60, A. A. Mahamad, “High
Efficiency Solar Air Heater”, 71–76, copyright 1997 with
permission of Elsevier Science.
Chapter 15
beneath the pot inside the house.170 In another, vacuum
tube heat pipes are hooked to the oven.171 Solar cookers of-
fer a way to compensate for fuelwood shortages in devel-
oping countries and to relieve pressure on forests. Wood
and crops can be dried faster in a solar tunnel than in the
open air.172 Solar energy has been used to heat swimming
pools.173 Solar-powered water sterilizers used in Hawaii
and other places heat the water to 65°C.174 It is possible to
desalinate water with solar energy175 at half the price
of evaporative desalting with fossil fuels or by reverse
osmosis.176
There is virtually no use of passive solar heating and
cooling in Delaware. Although the small additional cost in
building this way is offset by savings in fuel costs after a
few years, many buyers may opt for the lowest initial cost
(but higher long-term cost). Some buyers will spend money
for extras, such as decks and hot tubs, but may know noth-
ing about the advantages of passive solar heating and cool-
ing. In contrast, Davis, California, has a building code that
almost requires passive solar heating and cooling. It is also
a place where it is safe to ride bicycles. Each weekday
morning, children put on their safety helmets and ride their
bikes to school.
C. Refrigeration with Solar Energy
Cooling by absorption refrigeration was discussed in Chap.
3. Solar energy can be used as the heat needed to power the
system. (Biogas can also do so.) The best system seems to
be one using lithium bromide–water, although it is limited
to O°C as the lowest temperature.177 The ammonia–water
system can go to lower temperatures, but is less efficient.
Numerous other materials are being tested in the search for
cheap, efficient systems. These include other lithium salts,
with or without zinc salts,178 polyethylene glycol dimethyl
ethers with chlorofluorocarbons,179 charcoal with
methanol,180 active carbon and water with a zeolite,181
granular calcium chloride with ammonia,182 and strontium
chloride with ammonia.183 The reactions in the last system
(15.1) are
night
SrCl2-NH3  7 liquid NH3 OMM
MMH SrCl2-8NH3  heat
day
(15.1)
A solar ammonia–carbon ice maker produced 500 kg ice
per day.184 Electricity from photovoltaic cells can also be
used to run refrigerators.185 Photovoltaic cells were also
used to power a thermoelectric device using the Peltier ef-
fect (which involves passing a current through a junction of
two dissimilar metals) to reach 3°C.186 The system has
no moving parts and is small, lightweight, reliable, noise-
less, portable, and is potentially low-cost when mass-pro-
Energy and the Environment
duced. The best current material for the Peltier effect,
Bi2Te3, still requires too much energy to make this system
competitive with most compressor-driven refrigeration.
The search is on for materials with two to three times as
much effect.187 If these can be found the conventional re-
frigerator may become a thing of the past.
D. Heat Storage
The intermittent nature of sunlight requires that there be
some means of storing heat at night and on cloudy days. A
mass of concrete or masonry is used for that purpose in pas-
sive solar homes. The heat can also be stored in beds of
rock,188 in the soil,189 in tanks of water,190 or in aquifers.191
Some of these are for seasonal storage. In one case, 30-m
vertical heat exchangers placed in the ground achieved
storage efficiencies of 70%. Water pits of concrete lined
with stainless steel or high-density polyethylene and insu-
lated with mineral wool have been used in Germany for the
seasonal storage of solar heat. One being built in Hamburg,
with 3200-m2 collectors and 4500 m3 of water, is expected
to supply 60% of the heat needed in the winter by 120
houses. Another is being built to service 570 apartments.
The average temperature for one in Italy on July 31, 1996
was 69.3°C and was expected to reach 80°C by the start of
the heating season.192
For indoor storage, it is desirable to have storage mate-
rials that take up less space, but may cost more. This can be
accomplished by materials that undergo phase changes, de-
hydration, and such.193 The compound must change state in
a useful temperature range, have a relatively high latent
heat per unit volume, and be cheap. Inorganic ones are non-
flammable, but may be corrosive. Organic compounds
probably would not be corrosive, but could burn. For ex-
ample, calcium chloride hexahydrate melts at 25°C, so that
it melts by day and freezes by night. But it, along with other
hydrates such as magnesium chloride hexahydrate and
magnesium nitrate hexahydrate, tend to supercool.194 The
use of 0.5% sodium metaborate dihydrate with a eutectic
mixture of magnesium chloride hexahydrate and magne-
sium nitrate hexahydrate reduced the supercooling from
16°C to 2°C. Another problem is that the anhydrous salt
may settle out and not rehydrate properly. This can be min-
imized by using thickeners such as 3% acrylic acid copoly-
mer with sodium sulfate decahydrate containing 3% borax
to prevent supercooling.195 Carboxymethylcellulose
(2–4%) was also used with sodium acetate trihydrate con-
taining 2% potassium sulfate.
The hydrates or phase-change materials may also be
incorporated in other materials. Calcium chloride hexahy-
drate has been used to fill pores in silica, alumina, carbon,
and metals.196 This may be a way of eliminating problems
451
of settling of anhydrous salts. If a phase-change material
is incorporated into the walls or floors of a building, the
need for a separate storage vessel is eliminated. A mixture
of butyl palmitate and butyl stearate, melting at 21°C, was
put into wallboard at a level of 23%.197 In another case, a
mixture of lauric and myristic acids was used in wall-
board.198 Methyl palmitate, containing some methyl
stearate, has also been used.199 Neopentyl glycol, which
undergoes an endothermic transition from a monoclinic to
face-centered cubic crystal at 39°C, has been used in
floors.200 A little graphite (1%) is used to help nucleate
the process.
When higher-temperature heat is available, other sys-
tems are possible. A school in Munich, Germany, dehy-
drated 7 metric tons of zeolites using 130°C steam in the
district heating system during off-peak hours, then passed
moist air over them in the day to recover the heat.201 Pellets
of calcium hydroxide containing zinc, aluminum, and cop-
per additives were dehydrated to calcium oxide using solar
heat from a solar concentrator; then the reaction was re-
versed to recover the heat.202 Zeolite 13X has been used to
store carbon dioxide obtained from the decomposition of
calcium carbonate at 825°C (15.2).203 Such temperatures
are available with solar furnaces (where a whole field of
mirrors focus on the reaction vessel).
825°C
MMH CaO  CO2
CaCO3 OMM (15.2)
The reaction is free of toxicity and corrosiveness, has no
side reactions and the raw material is cheap. More work is
needed in this area to find reactions that work well with
low-grade waste heat and with heat from flat plate or
parabolic solar collectors.
E. Lighting
Compact fluorescent lamps use about one-fourth as much
energy as the incandescent bulbs that they replace.204 Such
lamp replacement has been a common part of many energy-
conservation campaigns. For outdoor lighting, low-pres-
sure sodium lamps are eight times as efficient as incandes-
cent lamps, three times as efficient as mercury lamps, and
40% better than high-pressure sodium lamps.205 The yel-
low color of the outdoor light should not interfere with
most outdoor activities. A sulfur bulb (the size of a golf
ball), which gives off four times as much light as a mercury
lamp at one-third the cost, is being tested by the U. S. De-
partment of Energy.206 The light produced by irradiating
sulfur in argon with microwaves is similar to sunlight, but
it has very little energy emitted in the infrared and ultravi-
olet ranges. It puts out as much light as 250 100-W–incan-
descent bulbs. When used with light pipes, it could illumi-
nate large areas of stores, offices, and outdoor areas. The
452
cost of illuminating shopping centers and factories in the
United States is 9 billion dollars each year.
New luminescent materials are being studied for light-
ing and for displays.207 A xenon plasma can be up to 65%
efficient, compared with low-pressure mercury lamps,
which are about 30% efficient. The ultraviolet light from
the plasma can be converted to red light with a
LiGdF4:Eu3 phosphor in a process during which one pho-
ton of vacuum ultraviolet radiation is converted to two vis-
ible photons.208 If suitable phosphors can be found to pro-
duce visible light, this could result in elimination of
ordinary fluorescent lamps, which all contain mercury (see
Chap. 4). It would increase the efficiency of current xenon
lamps used in simulating sunlight in accelerated testing of
materials and as sources of light for fiber optic illumina-
tion.209 Workers at Los Alamos Laboratory have made flu-
orescent lamps in which the mercury has been replaced
with a carbon field emitter of electrons.210 Blue light-emit-
ting diodes based on gallium nitride can be used to produce
white light.211 The combinations of phosphors needed for
this are being optimized. They are more energy-efficient
than halogen lamps. Organic light-emitting diodes are also
being studied.212 These might remove the need for gallium,
which is not a very abundant element.
People prefer to work under natural lighting, rather
than under artificial light. They also like to be able to see
out of the windows. “Daylighting” can bring natural light
to more areas in a home or office. It involves the use of
skylights, atria, and such, to bring light to more indoor ar-
eas.213 Windows in interior walls also help. These can be
empty or of transparent or translucent plastic or glass. In
former years, skylights were more common on factories.
Skylights with vertical panes of glass situated on homes
are sometimes called clerestories. Light from skylights
can be brought to various parts of the home through light
pipes.214 In some ways, they may resemble a periscope on
a submarine. The pipes (typically 0.25 m in diameter) can
be hollow plastic tubes of a polymer, such as poly(methyl
methacrylate). This polymer is used in optical fibers for
carrying light short distances from a central bulb to nu-
merous outlets, as in the instrument panel of an automo-
bile. The principle is one of total internal reflection. Light
striking the surface at less than the critical angle is re-
flected. Vacuum metallization of glass or plastic with alu-
minum, or other methods of making plastic mirrors, might
allow a variety of plastic substrates to be used.215 (Light
pipes might allow the lighting of buildings with fewer,
more powerful, but more efficient, bulbs.) Mirrors placed
at the upper section of a window can be used to bring
more light to the ceiling and to corners of rooms.216 Day-
lighting reduces the need for air-conditioning by eliminat-
ing the heat from unnecessary lamps. In one office build-
Chapter 15
ing in Brussels, this technique reduced energy consump-
tion by 60%.217
Windows can let in too much heat in the summer and let
too much escape at night and in the winter. These problems
are being approached in several ways.218 One is the use of
low-emissivity coatings that allow visible light to pass but
reflect infrared light. These thin coatings consist of metal
oxides or noble metals put on in a variety of ways.219 A
150-nm (one-fourth the wavelength of the average visible
light) film can be used for this purpose. One of the most
common coatings consists of indium tin oxide. It can be put
on the glass in a variety of ways. One way is to spray a so-
lution of tin(IV) chloride, indium(III) chloride, and some
fluoride ion on to a glass surface at 400–700°C. The trace
of fluoride eliminates haze. Dual nozzles can also be used
with tin(IV) chloride and nitrogen in one and water plus ni-
trogen in the other. A widely used system uses a layer of
silver between two layers of tin oxide. One way to make
this is by magnetron sputtering, using three sputtering
chambers. This involves a glow discharge through argon
containing some oxygen at 103 to 102 mbar, with some
source of tin or silver and permanent magnets below the
source plate. Vacuum evaporation, with or without an elec-
tron beam, is another technique for putting on the coat-
ings.220 Dip coating, followed by firing is also possible.
Mixed alkoxides plus water can be used in this method by
the sol–gel approach. Coatings of zinc sulfide (15 nm) over
silver (20 nm) have also been used.221 The silver can be re-
placed with aluminum (10 nm) with some loss of effi-
ciency. A possible problem with the use of indium oxide-
containing coatings is the limited amount of indium
available. About 120 tons of indium is produced in the
world each year.
Efforts are underway to produce “smart windows” that
will react with sunlight to keep out excess light. Pho-
tochromic222 sun glasses can be made by heating the lens
in a bath of molten silver nitrate plus silver chloride at
400°C for 4 h, followed by further heating at up to 660°C.
The silver chloride put in this way is converted to silver
metal in sunlight and then reconverted to silver chloride
when the light is removed. It is possible that this method
could be extended to windows. As mentioned in Chap. 7,
some polymers show inverse solubility in water. Thus, a
polymer blend of polypropylene oxide and poly(styrene-
co-hydroxyethyl methacrylate) has been used in a win-
dow.223 When sunlight heats up the window, the polymers
precipitate preventing entry of too much light. A com-
mercial material of this type called Cloud Gel is under de-
velopment.224 Systems are being developed that will not
freeze in the winter.225
A great deal of effort is going into developing elec-
trochromic226 windows that can be darkened by application
Energy and the Environment
of an electric current. Such systems are commercial in car
mirrors now. The electrochromic material is put on one
sheet of glass separated from the counterelectrode on an-
other sheet of glass by a solution of electrolyte. Current ef-
forts are directed toward increasing the durability over
many cycles and decreasing the cost and the response time.
Two of the most used electrochromic materials are tung-
sten(VI) oxide and Prussian blue (a ferric ferrocyanide).227
The former works by reduction to the intensely blue tung-
sten(V). The latter forms the intensely blue Fe(II)
[Fe(III)(CN)6] from colorless Fe(II)[Fe(II)(CN)6]2. The
tungsten oxide varies in efficiency with the method of
preparation. It can be put on the glass by evaporation, sput-
tering, chemical vapor deposition, spraying, the sol–gel
method, or others, with the resulting film varying in poros-
ity, density, and morphology.228 Tungsten(VI) oxoalkox-
ides and -diketonates have been used in chemical vapor
deposition.229 Inclusion of some fluoride ion in it leads to
rapid dynamics and good durability.230 Another method in-
volves dipping an indium–tin oxide-coated glass in an
aqueous solution of sodium tungstate and hydrogen perox-
ide, followed by heating.231 This improved the response
time. However, heating it too hot caused crystallization,
which reduced the performance. Putting in some lithium
(Li/W  0.14) by evaporation in an electron beam gave a
film with good reversibility and coloration efficiency.232
The transmission of light dropped from 80 to 20% when an
electric current was applied. Polyaniline and polyalkylthio-
phenes have been tested with the tungsten oxide.233
Other materials being investigated include ferrocene
with a bipyridinium salt,234 niobium oxide,235 nickel oxo-
hydroxide,236 and cobalt oxohydroxide.237 The last is pale
yellow in the reduced state and dark gray in the oxidized
state. A typical electrolyte is lithium perchlorate in propy-
lene carbonate. Solid electrolytes, such as a lithium salt
(perchlorate, tetrafluoroborate, or triflate), in a polyepox-
ide238 or in a polyvinyl chloride gel in ethylene carbon-
ate–propylene carbonate,239 lithium iodide in polyvinyl bu-
tyral,240 and Nafion H (a polymeric perfluorocarbon-
sulfonic acid),241 have also been tested. Some other sys-
tems use suspended particles between two panes of
glass.242 When the particles are aligned by an electric field,
the window becomes transparent. Combination photo-
voltaic–electrochromic devices are under study.243
Much heat is lost through glass windows, even those
that are double-glazed. An improvement is the double-
glazed window with a vacuum inside.244 Low emissivity
glass was used with minute pillars inside to prevent col-
lapse. The system was still good after 1 year.245 Other sys-
tems use transparent insulation in the windows.246 Some of
the best use silica aerogels (very light silica gel) are made
by the sol–gel method from tetraalkoxysilane (15.3).247
453
Si(OCH3)4  4 H2O → 4 CH3OH
(15.3)
 Si(OH)4 → (SiO2)n
In one case, the gel was washed with methanol to remove
the water, then with amyl acetate, and finally dried with su-
percritical carbon dioxide. Drying in an oven caused the gel
to collapse to a denser xerogel. Inclusion of some fluoride
in the process gave excellent transparency. When 1.5 to
2.0-cm layers of these aerogels, which contained up to 98%
porosity, were placed in a double-glazed window with
some vacuum, thermal losses were six times less than in the
usual double-glazed window. This makes them as good as
the usual insulated wall in reducing heat losses. Translu-
cent aerogel granules have been made by BASF using a
double-spray nozzle with aqueous solutions of sodium sil-
icate and sulfuric acid. Although these starting materials
are cheaper, the drying with supercritical fluids is still ex-
pensive. More recent work has found an additive that al-
lows an aerogel, dried under normal conditions of temper-
ature and pressure, to spring back to its original shape
after drying.248 Reaction with chlorotrimethylsilane,
methyltrimethoxysilane, or aryltrimethoxysilane, has been
used to eliminate the need for supercritical drying. Hoechst
was developing an aerogel that does not require drying
with a supercritical fluid249 and has sold the process to
Cabot.250 The wet gel made from sodium silicate is treated
with an organic compound before drying at atmospheric
pressure. The gel has permanent water-repellent properties.
Its thermal conductivity is about one-third that of of con-
ventional insulation, such as polyurethane and polystyrene
foams. The brittleness and moisture pickup of silica aero-
gels can be reduced by starting with an alkyltrimethoxysi-
lane instead of a tetraalkoxysilane.251
Aerojet has made organic aerogels with densities of
0.1–0.2 g/mL3 for use in insulators and capacitors.252
Transparent macroporous monoliths have also been made
by polymerization of trimethylolpropanetrimethacrylate
using toluene, ethyl formate, and other liquids as poro-
gens.253 Poly(alkyl methacrylates) have good resistance to
outdoor weathering and can be used in windows.
Glass capillaries mounted perpendicular to the panes of
glass have also been used as transparent insulation.254 Fifty
years ago, hollow glass bricks were used to let light into
buildings. For places where it is not necessary to see out or
to have ventilation, they would seem to offer less loss of
heat than the usual windows.
The goal of many of these systems is to have automatic
control, so that a person does not have to adjust anything
with the time of the day or the season of the year. Low-
emissivity coatings for glass keep the heat from the sum-
mer sun out of the house, and keep heat in the house in win-
ter. Yet there are times when letting the heat in would be a
454
help in heating the building. Plain glass plus curtains con-
trolled by photocells and temperature sensors might be
used. A light roof is needed to reflect heat in the summer,
but a dark one may be needed to pick up heat in winter. Au-
tomating this transition would require reversible panels or
a device that would be black, yet would be covered with a
white pigment slurry in the summer. To avoid snow and ice
covering photovoltaic cell arrays in the winter, the panels
may be mounted on the vertical walls of the building. There
may also be conflicts between shade from trees to reduce
the heat on a building in the summer and photovoltaic cell
arrays to generate electricity for air-conditioning.
III. RENEWABLE ENERGY FOR
ELECTRICITY AND TRANSPORT255
A. Alternative Fuels256
Various alternative fuels for motor vehicles have been sug-
gested as a way of reducing air pollution. Those that are
still derived from coal, natural gas, or petroleum will do
nothing to mitigate the release of greenhouse gases that
lead to global warming. A bus powered by natural gas is
less polluting than one using diesel fuel. An electric car257
transfers the pollution to the power plant where the elec-
tricity is generated and where it may be easier to control. If
the electricity is made in one of the power plants in the mid-
western United States that was grandfathered by the Clean
Air Act and not required to clean up the stack gases, then
pollution might be higher with the electric car than with
current ones burning gasoline. If the electric cars use
lead–acid batteries, lead loss in mining and processing, as
well as recycling, must be kept low.258 If the electricity is
made by hydropower, wind power, photovoltaic cells, or
other renewable means, then the electric car would reduce
both air pollution and global warming. The use of photo-
voltaic cells on the roof and hood of the car has been sug-
gested.259
Methyl ether produces less soot and nitrogen oxides
when used as a fuel in diesel engines.260 It may be a way
for trucks with diesel engines to meet the new particulate
standards in the United States. It is made from synthesis gas
(15.4).
225°C
CO  2 H2 → CH3OH →
HMnW12PO40
under CO
(15.4)
CH3OCH3 CH3COOCH3
 including that from poultry farms. In North Carolina, the
96% 4%
The synthesis gas is usually made by treating methane or
petroleum with steam at high temperatures. It can also be
made from biomass; thus it could help reduce global warm-
ing. The methanol made from biomass in this way is a pos-
Chapter 15
sible fuel for cars. The problem is that at the current level
of use of cars and trucks, it would take huge amounts of
biomass.
Some of the carbon dioxide produced by burning fuels
could be converted into ethanol for use as a fuel
(15.5).261
Rh Se/TiO
CO2  H2 →
10
350°C
2
CH3CH2OH 83% selectivity
(15.5)
To be effective in reducing climate change, the hydrogen
would have to be produced by a renewable route (e.g., elec-
trolysis of water with electricity from a renewable source).
Almost all of it is made from synthesis gas derived from
fossil hydrocarbons today. Ethanol is also made by the fer-
mentation of sugars derived from corn and other sources
(as discussed in Chap. 9).262 It is cost-competitive in the
United States only because of a government subsidy, which
some persons consider to be “corporate welfare”.263 Cur-
rent pricing does not take into account the costs of envi-
ronmental degradation. Much current research is directed
toward improving the process to make it competitive, even
under the current pricing system. The preparation of diesel
fuel by the alcoholysis of plant oils264 to give, for example,
ethyl oleate from rapeseed oil, was also described in Chap.
9. This biodiesel fuel produces less particulate matter on
combustion than diesel fuel from petroleum.265 By the cur-
rent pricing system, this biodiesel fuel is two to three times
as expensive as diesel fuel derived from petroleum. Both
ethanol and ethyl oleate produced by these routes are al-
most free of sulfur. They are relatively nontoxic and, if
spilled, biodegrade quickly. High oleic vegetable oils can
be used as lubricants in place of mineral oils.266
Methane can be produced by anaerobic fermentation.
This is often performed in sewage-treatment plants where
the methane is used as fuel to dry the sewage sludge. This
biogas can also be produced from plant and animal wastes
on the farm or at home. China has 5 million such digesters
and India has 1–2 million.267 These provide fuel for cook-
ing and electric power generation. The residue from gener-
ation of the biogas is used as fertilizer. The pollution of
streams and lakes from the runoff of fields with too much
manure spread on them could be eliminated by the use of
biogas generators. (In Delaware and Maryland, fish kills by
toxins produced by Pfiesteria, a dinoflagellate, have been
traced to overenrichment of streams by agricultural runoff,
problem was runoff from hog farms. Hog farms in the
Netherlands also have problems with runoff.) It has been
suggested that these wastes be used to produce biogas,
which could then be used to heat the chicken houses in win-
ter. The biogas could also be used for cooking and for heat-
Energy and the Environment
ing and cooling the farmer’s house and nearby houses. If
too much gas was produced in some seasons, it might be
compressed into a truck for transport and sale elsewhere.
These animal wastes might also be used in substrates on
which edible mushrooms are grown. Horse manure is used
for this purpose in the mushroom-growing areas of south-
eastern Pennsylvania.
Landfills in the United States produce 8.4 million met-
ric tons of methane each year. The gas from 750 landfills
could be recovered economically, but only in 120 was it ac-
tually collected in 1995.268 By 1998, the number had grown
to 259.269 (The landfill in Wilmington, Delaware, will sup-
ply gas to the electric power plant a mile away for 20
years.270) Any carbon dioxide and hydrogen sulfide impu-
rities in landfill gas are removed before the gas is burned
for fuel.271
Biomass can also be used for energy.272 In 1999;
biomass supplied 3% of the energy used in the United
States.273 Over 2 billion persons in the world rely on
biomass fuels.274 Energy plantations, preferably on land
unsuited for other crops, could provide 600 billion kwh of
electricity at $0.04–0.05/kwh, according to one estimate.
Most experiments use fast-growing poplars and willows or
switchgrass (Panicum virgatum). Switchgrass needs little
fertilizer or herbicides and can be harvested twice a year.275
The European system of coppicing may be suitable for har-
vesting the biomass from the trees. The tops are cut off ev-
ery few years, leaving the stumps to resprout. Cutting sim-
ilar to a hedge might also be suitable. Industrial coppicing
for wood for British power plants involves machine har-
vesting every 3 years.276 To prevent loss of soil fertility, the
ashes from the power plant would have to be spread on the
ground of the plantation at intervals. Burlington, Vermont,
has a 200 ton/day biogasification plant that can use wood,
crop residues, yard waste, and energy crops to produce
electricity at $0.055/kwh.277 The gas produced by pyroly-
sis at 1500°F is a mixture of methane, carbon monoxide,
and hydrogen. The residual char is used to provide the heat
for the pyrolysis. The gases and liquids obtained from
biomass by pyrolysis or other means can be upgraded by a
variety of catalytic methods, including cracking with
zeolites.278
B. A Hydrogen Economy
Hydrogen has been proposed as a clean fuel that produces
only water on combustion.279 Even, some members of the
U. S. Congress have pushed for more research in this
area.280 Almost all hydrogen produced today (96%) is
made by steam reforming of natural gas or petroleum.281
For a sustainable future, the hydrogen must come from re-
newable sources.282 The steam reforming reaction can also
455
be applied to the methane in biogas or in the gas obtained
by the pyrolysis of biomass. The water–gas shift reaction
can then be run on the carbon monoxide (15.6) in the py-
rolysis gas to produce more hydrogen.
Fe catalyst
CO  H2O →
350400°C.
CO2  H2 (15.6)
In addition to the method of pyrolysis used in Burlington,
Vermont, there are other methods. One produces a bio-oil
that is then subjected to steam reforming to produce hy-
drogen.283 Wet biomass, such as water hyacinths and cat-
tails grown in tertiary wastewater treatment ponds, can be
gasified in supercritical water using a carbon catalyst to
produce a mixture of hydrogen, carbon monoxide, carbon
dioxide, and methane containing a little ethane and
propane.284 Treatment of wet cellulose with a nickel cata-
lyst at 350°C for 1 h recovered 70% of the hydrogen in the
cellulose, together with carbon dioxide and some
methane.285
Only 0.5% of the hydrogen used today is produced by
the electrolysis of water.286 Hydrogen produced in this way
costs four times more than that made from petroleum and
natural gas. Cheap electricity from renewable sources is
needed to encourage the production by electrolysis. The
electricity generated by photovoltaic cells can be used to
electrolyze water to produce hydrogen. It might cost less
and use less equipment if both steps could be run in one ap-
paratus. Photoelectrochemical generation of hydrogen
from water287 has been performed with up to 18% effi-
ciency.288 It has been carried out with a stacked gallium ar-
senide–galium indium phosphide cell with 12.4% effi-
ciency using sunlight.289 Systems under study include
niobates (A4Nb4O17, where A is calcium, strontium, lan-
thanum, potassium, or rubidium) used with cadmium sul-
fide or nickel,290 cerium(IV) oxide,291 copper(I) oxide,292
and titanium dioxide.293 Dye-sensitized solar cells, using a
ruthenium bipyridyl complex with tin and zinc oxides,
gave about 8% efficiency in direct sunlight.294 A seaside
power plant in Japan has used solar energy to produce hy-
drogen from water, then used the hydrogen to reduce car-
bon dioxide to methane over a nickel–zirconium catalyst at
300°C.295 The methane was burned to generate more elec-
tricity. It would be more direct to generate the electricity
with the photocell.
Microorganisms contain hydrogenases that allow them
to produce hydrogen.296 Anabaena variabilis has been used
in a photobioreactor to produce hydrogen.297 This system
has been proposed as a way to utilize carbon dioxide from
power plants. The biomass produced could be converted to
more hydrogen through synthesis gas, as described earlier.
The search is on for more efficient strains or other organ-
isms. A combination of enzymes from thermophilic bacte-
ria (Thermoplasma acidophilum and Pyroccoccus furio-
456
15.4
sus) has been used to convert glucose to gluconolactone,
which hydrolyzes to gluconic acid (15.4), with 100%
selectivity.298
A mixed culture of Clostridium butyricum and Enter-
obacter aerogenes makes more than 2 mol of hydrogen
from glucose, the other products being carbon dioxide and
a mixture of acetic, butyric, and lactic acids.299 The glucose
might be obtained from the hydrolysis of cellulose or
starch. The photodehydrogenation of ethanol to acetalde-
hyde over a heteropolyacid also gives 100% selectivity.300
If either of these is used on a large scale, additional uses
will have to be found for the gluconic acid and acetalde-
hyde; or they can be converted to carbon dioxide and more
hydrogen via synthesis gas.
Storage of the hydrogen fuel poses some problems. The
gas can be compressed for storage at fixed sites. For use in
vehicles, this would add considerable weight in the form of
steel tanks. Various methods that would allow more hydro-
gen to be stored in lighter-weight tanks are being studied.
Hydrogen can be stored in a cadmium-exchanged zeolite
rho301 (71 mol/g) and in buckytubes.302 Potassium-doped
carbon nanotubes took up 14% of their weight of hydrogen
at room temperature, retaining over 90% of their capacity
over 90 cycles.303 However, the lithium-doped carbon nan-
otubes were preferred because they were stable to air at
100°C, whereas their potassium-doped counterparts caught
fire under these conditions. Graphite nanofibers took up
65% of their weight of hydrogen at room temperature un-
der 120-atm pressure.304 There may be problems in scaling
these up. Cadmium is a toxic metal and the others may be
hard to make on a large scale. Hydrogen storage alloys,
such as LaNi5, have been studied extensively.305 LaNi5 can
pick up enough hydrogen to form LaNi5H6.7. Iron/titanium
hydrides have also been studied.306 The container cost was
estimated to be high ($3300–5500). It would take 20–30
Chapter 15
min to refuel a car using this system. (Similar systems con-
taining two different materials that absorb hydrogen at dif-
ferent temperatures; e.g., ZrCr Fe1.4/LaNi5, have been sug-
gested for recovery of heat from industrial wastewater at
100°C.307 Hydrogen is released when one hydride is
heated by the wastewater. Heat is released from the other
bed as hydrogen is picked up.)
Other systems propose to store hydrogen by reversible
chemical reactions. Ammonia has been suggested as a
fuel,308 either burned as such or thermally dissociated to re-
cover the hydrogen. Benzene could be hydrogenated to cy-
clohexane, which could be shipped to a destination where
it would be dehydrogenated to recover the hydrogen.309
Because benzene is a carcinogen, it might be better to use
toluene or naphthalene. Hydrogenation of fullerenes for
hydrogen storage has also been proposed.310 Methanol has
been suggested for the storage of hydrogen. It can be dehy-
drogenated to methyl formate, which can be converted
back to methanol by hydrogen produced by the electrolysis
of aqueous sodium chloride in the presence of the for-
mate.311 The process is said to be 20% cheaper than trans-
porting liquid hydrogen. Any reaction that is used needs to
store a lot of hydrogen per unit weight in a reaction that is
fully reversible without side reactions.
The first hydrogen filling station has been set up in
Hamburg, Germany.312 Hydrogen-fueled vehicles are 70%
efficient compared with about 23% efficiency for ones with
a conventional fuel and engine.
C. Fuel Cells313
Hydrogen would be burned in a fuel cell to power an electric
vehicle. The only product would be water. This is the reverse
of the electrolysis of water to produce hydrogen and oxygen.
The system is not subject to the Carnot cycle, which limits
Energy and the Environment
efficiency in the usual electric power plants,314 and 60%
electrical efficiency can be obtained. Demonstration cars
and buses have been built.315 The fuel cells fit in the same
space as the present diesel engine in the bus. An aircraft
powered by hydrogen is being planned.316 Hydrogen is
lighter than present jet fuel, but requires four times as much
storage space. The lighter fuel may permit more payload if
the tanks that store the hydrogen do not weigh too much. The
prototype minivan used tanks made of carbon fiber-rein-
forced plastic mounted on the roof. It was able to travel 150
miles between refuelings. The use of methanol, ethanol, nat-
ural gas, or gasoline will require a re-former on board to con-
vert the fuel to hydrogen. Such systems are being studied.317
Such cars may achieve twice as many miles per gallon as
cars with internal combustion engines. A problem that is be-
ing overcome is that the traces of carbon monoxide in the
hydrogen from re-forming poison the catalyst. Fuel cells can
now be run directly on butane, ethane or propane.462
The principal types of fuel cells being developed for var-
ious uses are (a) molten carbonate, (b) solid oxide, (c) poly-
mer electrolyte, and (d) phosphoric acid. A typical molten
carbonate is a mixture of lithium and potassium carbonates
at 650°C running at 60% efficiency. If by-product heat can
be utilized, then the total energy efficiency will be higher.
Fuel cells can run on landfill gas even if carbon dioxide is
present. They can have single-cell lifetimes of 30,000 h.318
Many cells are stacked in series to obtain the desired volt-
age. Solid oxide systems, such as zirconium and cerium ox-
ide mixtures,319 can be run at 600°C or higher. One 25-kw
prototype ran 13,194 h before a scheduled shutdown. A per-
fluorinated sulfonic acid, such as Nafion, is used as a solid
electrolyte in some fuel cells that are the most likely to be
used in vehicles.320 No liquid electrolyte is present. A plat-
inum catalyst for the reaction is used. Concentrated phos-
phoric acid at 200°C is used in some fuel cells. One in
Tokyo ran continuously for 9477 h before being shut down
for scheduled service. Stationary fuel cells have advantages
for electric power production. They can be nonpolluting.
Transmission losses are reduced over those of conventional
systems when the fuel cells are located near where the
power will be used. Fuel cells come in modules, so that it is
easier to expand the production of power than it is with a
conventional electric plant using fossil fuels. Before fuel
cells come into widespread use, their cost must be reduced.
D. Solar Thermal Systems321
Heat from the sun can be concentrated by parabolic
troughs, parabolic dishes, or by mirrors to produce steam
for generating electrical power. These can be used to heat a
fluid at the focal point of the parabola from which the fluid
is then pumped to the steam generator. The heat can also be
457
aimed at a central receiver. The central receiver allows
higher temperatures to be reached. These systems can be
made to track the sun for greater efficiency. A 750-ha plant
in the California desert using parabolic troughs has oper-
ated for 10 years with more than 94% power availability. It
produces electricity for as little as $0.09/kwh. Further im-
provements, such as vacuum insulation for the heat-carry-
ing pipes, better absorbers, antireflective coatings, and
such, are expected to lower the cost of the electricity to a
level at which it can be competitive with that from conven-
tional plants that burn fossil fuel.
Solar absorbers of Mo/Al2O3 can be deposited on cop-
per-coated glass using two separate electron beams.322
These offer 0.955 absorbance at 350°C, when topped with
an antireflective coating of alumina. Another offers 90%
solar absorbance with low thermal emittance through
the use of a 50-nm Al2O3/10–12-nm: AlCuFe/70-nm
Al2O3–layered coating.323 The AlCuFe coating is applied
by ion beam sputtering. Cathodic arc chemical vapor depo-
sition of absorbant surfaces is reported to be faster than
other methods.324 The stainless steel–aluminum nitride
coatings put on by magnetron sputtering (mentioned ear-
lier) are stable to 330–400°C.325 Black cobalt oxide ab-
sorbers applied by electrodeposition are stable to 300°C,
but not to 400°C.326 Further research is directed at ab-
sorbers that will be stable at 500°C.
Parabolic dishes can produce higher-temperature steam
than parabolic troughs. The central receiver for a field of
mirrors (a heliostat field) usually contains a nitrate salt with
blackened particles used at up to 900°C. A plant in the Cal-
ifornia desert uses 2000 motorized mirrors aimed at a 91-m
metal tower containing molten nitrate salts up to 565°C. The
salt stays hot for 2–12 h after the sun goes down so that some
additional electricity can be generated after dark.327 Higher
temperatures, up to 1600°C or more, are possible using mag-
nesium oxide powder in argon as a heat-transport medium in
a black-lined receiver.328 This should increase the efficiency
of the system. Molten nitrate salts and ceramic bricks have
been used for heat storage so that some additional electricity
can be generated after the sun goes down.
A solar chimney was used to generate electricity in
Spain for several years. The 200-m chimney with a 45,000-
m2 collector area at the base was shaped like an inverted
funnel. Heat rising through the chimney produced wind
that ran the generator. The residual heat in the soil allowed
some additional electricity to be generated at night. Solar
ponds trap the sun’s heat in salt solutions. The temperature
gradient in the pond is used to run a heat engine (Stirling
engine) to generate electricity.329 They are relatively inef-
ficient. A temperature gradient between warm surface wa-
ter and cold deep water (of at least 20°C) in the ocean can
be used to drive a heat engine with ammonia or another ma-
458
terial as the working fluid.330 This has been done in Hawaii
where deep water is close to land. The nutrient-laden deep
water brought to the surface can be used for aquaculture to
derive additional benefits.
Beaming power to earth from solar power satellites has
also been suggested.331 Problems could occur if the incom-
ing beam missed the target receiver.
E. Photovoltaic Cells332
Photovoltaic cells convert light to electricity at the place
where it is to be used. There is no need for a central fa-
cility with a concentration of equipment or for long trans-
mission lines (as well as the losses of electricity in them).
The peak in the electricity generation may well occur on
the hot summer afternoon when the electrical system of
the community is strained and expensive supplemental
generators must be brought into service. Thus, its cost
should be compared with the cost of this supplemental
electricity in this situation. (In 1999, electricity from the
best photovoltaic systems cost about twice as much as
peak power from a conventional plant.) Photovoltaic sys-
tems are cost-competitive now in places remote from
power lines. Further research is needed to make them
cost-competitive in areas where an electric network is al-
ready in place. The current problem is that the most effi-
cient photovoltaic cells are expensive to produce and the
cheaper ones are not efficient enough. Photovoltaic sys-
tems use no toxic fuel, use an inexhaustible fuel, produce
no emissions, require little if any maintenance, and have
no moving parts. The United States produces 44% of the
world’s solar cells, Japan 24%, Germany 21%, and the
rest of the world 11%.333 The market for photovoltaic
cells is growing at the rate of 24%/yr.334
High-efficiency solar cells can be made from silicon
wafers cut from single crystals grown from a melt.335 One
of the most efficient systems is made by a series of steps.336
Its efficiency is 23.5% under 1 sun (1 sun means that no
mirrors are used to concentrate the light. Because mirrors
are cheaper than solar cells they are sometimes used.)
1. Diffuse boron tribromide into the back to produce
p-type silicon (i.e., with a deficiency of electrons
sometimes referred to as holes).
2. Texturize the front by selective etching through a
mask to produce a surface of inverted pyramids (to
maximize absorption by allowing light to hit twice).
3. Diffuse phosphorus oxytrichloride into the front
to form n-type silicon (i.e., with an excess of
electrons).
4. Passivate by thermal oxidation to form silicon diox-
ide on the surface.
Chapter 15
5. Metallize the front by vacuum evaporation to form
a Ti/Pd/Ag layer (to minimize reflection of light).
6. Metallize the back by vacuum evaporation of alu-
minum (to reflect light within the cell to maximize
absorbance).
7. Put on buried contacts in grooves cut by a laser (to
minimize losses due to shading by the grid).
8. For use outdoors, cells are usually encapsulated in
an ethylene–vinyl acetate copolymer.
9. Attach foundation, frame, cover glass, wires, and an
inverter to convert the direct current produced by
the cell to alternating current.
The number of steps needs to be reduced to reduce the
cost.337 One proposal is to coat both sides at once.338
Uncoated, untextured silicon may reflect as much as 36%
of the incident light. This can be reduced to about 12% by a
single coat of titanium put on by the sol–gel method, and to
3% by a double titanium dioxide coating.339 Other materials
for antireflective layers include silicon nitride,340 tantalum
oxide,341 radiofrequency-sputtered indium tin oxide,342 and
zinc oxide.343 Nanoporous poly(methyl methacrylate) al-
lows 99.3% of the incident light to pass through.344 A sulfur
hexafluoride–oxygen plasma has also been used to texturize
silicon surfaces.345 Abrasive cutting wheels have also been
used.346 The discoloration of the ethylene–vinyl acetate en-
capsulant can be reduced by stabilizers or by the use of a
glass that filters out the ultraviolet light.347
Polycrystalline silicon is cheaper than single-crystal sil-
icon. It can be made by slow casting of an ingot of silicon.
An 18.6% efficiency has been obtained in a cell made with
it.348 Amorphous silicon has a higher absorbance than crys-
talline silicon and can be used in thinner layers, down to
less than 1 m.349 It can be crystallized with a laser, but this
might require application of several layers to obtain the
thickness needed for a solar cell.350 Amorphous hydro-
genated silicon can be made in a plasma from silane and
methane.351 Such thin film cells352 can reach efficiencies of
9–10%. Rear reflectors increase efficiency by keeping the
light in.353 Unfortunately, thin-film cells have a lower effi-
ciency after a few years owing to diffusion of aluminum
from the contacts into the silicon. Some of the loss can be
restored by annealing at 150°C. Some of the loss can also
be avoided by using thermal insulation to keep the cell hot-
ter.354 If a triple junction cell (i.e., one containing the
equivalent of three stacked cells) is used, the efficiency can
be as high as 12.8%.355 Flexible plastic cells of amorphous
silicon have been made by automated roll-to-roll chemical
vapor deposition processes.356 Amorphous silicon on crys-
talline silicon has been used in an effort to decrease the
thickness of crystalline silicon needed.357 The cell effi-
ciency was 14.7–16%.
Energy and the Environment
There are some other thin-film devices that have equal
or higher efficiencies.358 Cadmium telluride in 1 to 2-m
films is 15–16% efficient.359 The most efficient (about
17–18.8%) thin-film cells have been made from
Cu(In,Ga)Se2.360 Cheaper routes that use fewer vacuum
processes are being explored, but the resulting cells are not
as efficient.361 The efficiency in both cases is limited by
any crystal defects that may be present.362 Various methods
of preparation are being studied in an effort to prepare films
with fewer defects.363 For the preparation of cadmium tel-
luride, these include sublimation, evaporation, chemical
vapor deposition, spraying, and electrodeposition. A film
free of defects has been obtained by spraying cadmium and
tellurium solutions containing phosphines on to a substrate
at temperatures higher than 250°C.364 Chemical vapor de-
position is often used to make gallium arsenide and other
materials for solar cells.365 An example is the pyrolysis of
the single precursor, Ga[(As-tert-C4H9)2]3, to form gallium
arsenide (15.7). It affords a safer preparation than routes
that use pyrophoric or very toxic substances such as
trimethylgallium, arsine, and such.
600–800°C
Ga(CH3)3  AsH3 → GaAs  3 CH4
(15.7)
InP has been prepared in a similar fashion at 167°C.366 A
way to avoid the use of poisonous hydrogen selenide is to
treat the copper–indium alloy with selenium vapor at
400°C.367
The band gap of a semiconductor is the energy needed
to promote an electron from a valence band to a conduction
band (i.e., to make an electron mobile).368 Typical band
gaps are silicon 1.2 eV, gallium arsenide 1.4 eV, cadmium
selenide 1.7 eV, cadmium sulfide 2.5 eV, and CulnS2 1.53
eV. The energy in visible light is 1.4–1.5 eV. For a good
photovoltaic cell, it is desirable to choose a material with a
band gap in or close to this range. A europium-doped cal-
cium fluoride crystal has been used to shift some of the
shorter wavelengths in sunlight to longer wavelengths
more suitable for silicon-based cells.369
Gallium arsenide is more efficient than most other semi-
conductors,370 especially when used in tandem with an-
other cell material that absorbs in another part of the solar
spectrum, so that more of the light can be used.371 Me-
chanically stacked GaSb/GaAs cells were 34% efficient at
100 suns and 30% at 40 suns.372 A tandem solar cell of In-
GaP/GaAs had a 30% efficiency at 1 sun.373 The possible
problem of a mismatch of the two different crystals can be
solved by inclusion of a flexible layer.374 A holographic
system focuses light, diverts the unwanted infrared radia-
tion, splits the light, and focuses the two bands on different
solar cells, one of gallium arsenide and the other of silicon
459
(Fig. 15.2).375 A 20-fold concentration of the light is ob-
tained. It will require a device to track the sun. It is de-
scribed as a “major breakthrough” that will make solar
power competitive with that from fossil fuels. The electric-
ity will be produced at a cost of $0.057/kwh compared with
a cost of $0.075/kwh in a conventional plant using pulver-
ized coal as a fuel. (Care should be used in comparing
prices, because they may vary with the time and place.)
A group in Switzerland has developed a photovoltaic
cell that can function as a window for a building.376 In one
example, a ruthenium pyridine complex photosensitizer is
attached to the titanium dioxide semiconductor by a phos-
phonate. An iodine-based electrolyte (Kl3 dissolved in
50:50 ethylene carbonate/propylene carbonate) is between
the panes. All the films are so thin that they are transparent.
The efficiency is 10–11%. Variants on such cells have in-
cluded fullerenes377 and polypyrrole.378 The use of solid
electrolytes will avoid problems that might occur if a seal
on a liquid electrolyte leaked.
Silicon has the advantages of being abundant and non-
toxic. Most other cells contain toxic metals or elements that
are not abundant and probably not cheap. If materials other
than silicon come into common use, some sort of collection
and recycling system will be needed to keep discarded cells
from ending up in incinerators and landfills where they
may be sources of pollution.379 (“Silicon Valley,” Califor-
nia has 29 Superfund sites.380)
Solar cells are being used for many purposes in many
places around the world: for heating and lighting homes,
lighting bus stops, pumping water, and many others.381
They can be used in place of the usual cladding or roofing
Figure 15.2 Schematic of a holographic systems to focus light
in solar cells. Reprinted from Sol. Energy, vol. 60, J. E. Ludman,
J. Riccobono, I. V. Semenova, N. O. Reinhand, W. Tai, X. Lo, G.
Syphers, E. Rallis, G. Sliker and J. Martin, “The Optimization of
a Holographic System for Solar Power Generation”, p. 1–9,
copyright 1997 with permission of Elsevier Science.
460
of a new building, which avoids some of the costs for the
usual materials used for these purposes.382 They may work
best if cleaned and serviced at intervals by an independent
serviceman or one connected with the local utility.383 Indi-
vidual home owners may forget to clean them. Self-clean-
ing modules based on the photocatalytic action of thin lay-
ers of titanium dioxide may be possible384 (see also Chap.
8). A home in Osaka, Japan, fed 77% of its photovoltaic
power into the grid between 10:00 AM and 2:00 PM on a clear
day in May.385 This suggests that 3 kw of photovoltaic
power on a house at this location would satisfy most of the
needs for the house and alleviate peak power demand. A
house in Florida with photovoltaic cells and white roof tiles
required 83% less energy to air-condition than a conven-
tional house.386 With more solar cells, it might not require
any energy from the electrical grid. It is also possible to uti-
lize both the heat and light of the sun with the solar array.387
A test house built in Freiburg, Germany, operated for 3
years without being connected with the local electrical
grid.388 Electricity from photovoltaic cells was used to pro-
duce hydrogen and oxygen by the electrolysis of water. The
hydrogen was stored at 28 bar. Electricity was stored in
lead–acid batteries or was obtained by reaction of the hy-
drogen and oxygen in a fuel cell. Catalytic combustion of
the hydrogen was used for cooking and space heating. The
house used passive solar heating as well as transparent in-
sulation in the windows. Its annual energy consumption
was 8.7 kwh/m2 compared with 110–140 kwh/m2 for a
standard German house. The only problem was that the liv-
ing room was a little cool. The builders of the house would
like a better method for long-term high-energy storage.
F. Other Sources of Renewable Energy
Other sources include hydropower, tidal energy, wave en-
ergy, geothermal energy, and wind.389 Further develop-
ment of hydropower390 is possible, for many existing dams
do not involve the generation of electricity. This may be
partly due to the small heads of water involved. The erec-
tion of new dams for this purpose involves tradeoffs, be-
cause natural biotic communities as well as agricultural
fields, houses, and towns are often lost in the process. The
wind was used more as a source of power in the past than it
is today. Before the days of rural electrification in the
United States, it was common practice to use windmills to
pump water for the farm. The Netherlands is famous for its
windmills of former years that were used to grind grain,
and such. Windpower is cost-competitive today in some ar-
eas.391 Part of the cost is offset because the land under the
turbines can be used for other purposes, such as farming
and grazing. Some new projects are producing electricity at
a wholesale price of $0.045/kwh.392 Wind farms are lo-
Chapter 15
cated in places where the wind blows fairly steadily, such
as mountain passes and at the seashore. The Great Plains of
the western United States has been suggested as a place for
wind farms. A 100 MW wind farm is planned for Min-
nesota and a 50 MW one for Iowa. The power of the wind
goes up as the cube of the wind speed. In 1994, California
had 15,000 wind turbines, generating enough electricity to
supply a city the size of San Francisco. They operated 95%
of the time. The 3600 wind turbines in Denmark supplied
3% of the country’s electricity. Globally, wind energy in-
stallations grew an average of 22%/yr from 1990 to
1999.393 In 1998, the wind energy industry was valued at 2
billion dollars. Both wind and sunlight are intermittent
sources of energy. A facility that uses both will be more re-
liable than one using either source alone.394 An Australian
sail boat combines the two.395 Interconnected grid systems
will be more reliable than single units.
Electricity is generated from steam in the ground in
places such as New Zealand, California, Nevada, Utah, and
Hawaii.396 Geothermal energy is also used to heat 80% of
the homes in Iceland. The steam and hot water from under-
ground reservoirs contain gases, such as hydrogen sulfide
and ammonia, as well as dissolved minerals that may con-
tain arsenic, mercury, vanadium, nickel, or others. The
geothermal plants can be polluting if these are discharged
at the surface. A better system is to reinject the used water,
not only to avoid the need to treat the water to remove pol-
lutants, but also to form more steam and to prevent land
subsidence. A plant is being built in the Imperial Valley of
California to recover 30,000 metric tons of zinc annually
before the reinjection of the used water.397 The plants at the
geysers near Santa Rosa, California have seen steam pro-
duction drop 10%/yr since the mid 1980s, despite reinjec-
tion of 31% of the water produced.398 A better system is to
use a closed loop with a working fluid other than water
(e.g., isobutane or pentane). This may also be better in uti-
lizing low-grade heat. Studies have also been made of us-
ing the heat of hot, dry rock to make steam to generate elec-
tricity. The temperature at the bottom of a 12,000-ft
borehole in New Mexico was 177°C (350°F). For produc-
tion of steam, it will probably be necessary to shatter the
rock at the bottom of the hole with explosives. Oil well-
fracturing techniques can also be used.
Tidal energy can be used to generate power in places
where the tidal range is fairly large.399 Power is generated
as the water goes in over a dam and again as the water comes
out over the dam. A plant in France uses this method. Pro-
posals have been made to use the exceptionally high tides in
the Bay of Fundy in Canada for this purpose. The waves in
the ocean are a much more general source of power, which
is largely untapped. A few prototypes have been tested for
the generation of power. The best may be those with the
Energy and the Environment
15.5
fewest moving parts. One system uses sand-filled ballast
tanks to keep the apparatus in place.400 As the wave passes,
air is expelled upward through turbines that generate elec-
tricity. As the water level drops, another air turbine will gen-
erate electricity. A wind turbine can be mounted on top, if
desired. The electricity from such a unit in Japan costs about
twice as much as that from an oil-fired power plant.401 Other
schemes use pistons actuated by the water to drive a gener-
ator. The up-and-down motion of a floating device anchored
to the bottom (a “bobbing duck”) could also be used to gen-
erate power. An underwater system utilizes the pressure dif-
ferences caused by the passing of the wave. The air in two
mushroom-shaped floaters that are each partially filled with
water is transferred between the two as the wave passes.402
Another system will use the motions of the sea to generate
electricity from piezoelectric polymers, such as poly(vinyli-
dene fluoride).403 (Pressure on a piezoelectric material gen-
erates an electric current.) Such polymers can also be used
to produce electricity from low-grade heat (e.g., water at
100°C).404 If such systems can be scaled up economi-
cally, they could increase the efficiency of conventional
power plants and reduce the thermal pollution of streams.
The challenge is to reduce the costs of the various forms
of renewable energy405 to where they can compete with
fossil fuels today. If the various environmental and health
costs were included in the price, the cost of electricity from
an unscrubbed coal-burning power plant would about dou-
ble. This new form of accounting would make it easier to
replace fossil fuels with renewable forms of energy.
G. Energy Storage
Because some of the sources of renewable energy are in-
termittent, it will be necessary to combine them with some
that are not, or find ways to store enough energy until the
source is again available. It might be possible to supple-
ment energy from the wind or the sun with energy from
biogas, biomass, or hydropower. This might require build-
ing an additional plant and the expense that goes with it. At
present, solar and wind power are supplemented with that
from natural gas and other fossil fuels.
Energy can be stored using pumped storage reservoirs,
compressed air in tanks, flywheels, or hot water.406 Fly-
461
wheels with electromagnetic bearings can be up to 90% ef-
ficient in storing and releasing energy.407 The possibility of
storing energy in highly extendible materials, such as rub-
bers is being studied.408 The storage of energy as heat, hy-
drogen, or in other chemical compounds was discussed ear-
lier. An additional possibility is to use light to form a
higher-energy compound that can later be reconverted to
the original compound with release of the energy. The re-
action must be 100% reversible over many cycles, should
work well with sunlight, and have a high quantum yield.
The most studied reactions of this type involve the conver-
sion of norbornadienes to quadricyclanes, which may be
small molecules or attached to polymers.409 A typical ex-
ample is shown in 15.5.
Storage of energy in batteries410 is common. The search
is on for batteries of common nontoxic materials that com-
bine light weight and compactness with high-energy den-
sity. The most common goal is a better battery for a motor
vehicle.411 For this use, it must be fully reversible over
many cycles and be relatively easy to recharge quickly. The
major candidates for electric vehicle batteries are shown in
Table 15.2.
The first three are commercially available today. The
nickel–cadmium battery has the disadvantage of using toxic
cadmium. The lead–acid batteries used in cars today weigh
too much and wear out too soon for widespread use in elec-
tric vehicles. The nickel–metal hydride battery appears to
be the best available today for general use.412 It is essen-
tially a nickel–hydrogen cell with a hydrogen-storing alloy,
such as LaNi5, as the anode with aqueous potassium hy-
droxide containing some sodium hydroxide and lithium hy-
droxide as the electrolyte.413 The active material in the cath-
Table 15.2 Candidates for Electric Vehicle Batteries
Range/charge Life Specific energy
Battery (miles) (yr) (W-h/kg)
Nickel–cadmium 65–140 8 45–55
Lead–acid 50–70 2–3 35–40
Nickel–metal 100–120 8 High 60s–70
hydride
Lithium ion 150–300 5–10 100–150
462
ode is nickel hydroxide. The overall reaction (15.8) in the
battery is (where M represents the hydrogen-storing alloy):
MMH NiOOH  MH
Ni(OH)2  M OMM (15.8)
Lithium batteries are being studied intensively owing
to their light weight and high-energy density.414 A cath-
ode of LiMnO2 has been suggested as a cheaper and less
toxic one than one of LiCoO2,415 but a little cobalt, as in
Li(Mn0.9Co0.1)O2, raises the storage capacity.416 Iodide
also increases the storage capacity, as in
Li1.5Na0.5MnO2.85I0.12.417 A battery with a tin(II) oxide an-
ode (Sn1.0B0.56P0.40AI0.42O3.6), which has 50% more ca-
pacity than the usual one with layers of carbon, is under de-
velopment.418 This cathode also avoids the problem of
dendrite growth on the anode. Cathodes of polypyrrole,
polythiophene, polyaniline, and other conducting polymers
have also been studied.419 One can use a poly[3(3,5-diflu-
orophenyl)thiophene] cathode and a poly[3(3,4,5-trifluo-
rophenyl)thiophene] anode with a polymer gel electrolyte
that has a conductivity higher than 103 S/cm in an all plas-
tic battery.420 The electrolyte is a lithium salt, such as per-
chlorate, hexafluorophosphate, hexafluoroarsenate, or tri-
flate, in solvents such as ethylene carbonate and propylene
carbonate. The electrolyte can also be a solid containing the
salt, such as polyethylene oxide or polypropylene oxide,
which yields an all-solid battery.421 A plasticizer can be
added to increase conductivity in the solid electrolyte. The
challenge is to increase the conductivity to the desired
range of 102 to 101 S/cm from the more usual 104 to
105 S/cm. An electrolyte film of a poly(epichlorohydrin-
co-oxirane) and poly(acrylonitrile-co-1,3-butadiene)
blend, swollen with a solution of 40% lithium perchlorate
in propylene carbonate, has a conductivity of more than
103 S/cm.422 A combination of polymer (15.6) with
lithium chlorate has a conductivity of 103 S/cm.423
Zinc–air batteries are also being studied for use in vehi-
cles.424 The anode consists of particles of zinc in aqueous
potassium hydroxide. The energy storage is about 160
Wh/kg. The range of the vehicle is expected to be about
15.6
Chapter 15
250–300 miles. A drawback is that the zinc must be separated
from the air electrode for recharging. The plan is to exchange
the discharged battery for a charged one at a recharging sta-
tion. An exchange system may be the best for many vehicle
batteries. It circumvents the problems connected with
charges that are too rapid. The system may be easier to apply
to buses than to private cars. An alternative for the latter is to
plug in the car while it is parked at a lot or in the garage at
home at night. A more difficult problem to solve is abuse of
batteries by drivers who accelerate and decelerate rapidly and
repeatedly, or who drive until the battery is almost dead.
Each year, the world uses 60 billion batteries made with
a zinc anode and a manganese dioxide cathode with an
electrolyte of potassium hydroxide. Substituting potassium
or barium ferrate for the manganese dioxide permits a
three-electron change instead of a two-electron one, in-
creasing the battery’s capacity by 50% or more.425 The
Fe(VI) battery is rechargeable, based on abundant starting
materials and environmentally benign.
V. USE OF LESS COMMON FORMS OF
ENERGY FOR CHEMICAL REACTIONS
Many chemical reactions must be heated to obtain adequate
rates. This can consume as much as one-third of the energy
in the starting hydrocarbon in some reactions used in refin-
ing petroleum. Reactions that must be run at high tempera-
tures with short contact times followed by quick quenching
are especially difficult. These are often run to low conver-
sion so that much recycling is needed.
The use of electricity, light, ultrasound, and microwaves
has advantages for many chemical reactions. The total en-
ergy input may be reduced. Selectivity may be improved.
The time required for the reaction can occasionally be
shortened dramatically, which would permit greater
throughput in a plant. Some of the reactions may not be
possible at all with simple heating. These forms of energy
are clean, meaning that unlike the usual catalysts, they re-
quire no separation at the end of the reaction, and there is
no waste from them to dispose of. These methods are un-
derused, probably because the usual chemists and chemical
engineers are unfamiliar with them. They should not be ne-
glected with the assumption that they will be more expen-
sive. They may actually be cheaper.
A. Electricity
Electricity is used on a large scale in the production of in-
organic compounds such as chlorine and sodium hydrox-
ide. It is used to refine metals such as aluminum and cop-
per and can also be applied to titanium.463 However, the
Energy and the Environment
15.7
only large-volume application in organic chemistry ap-
pears to be the hydrodimerization of acrylonitrile (15.7) to
form adiponitrile (200,000 tons/yr), which is then reduced
to the diamine or hydrolyzed to adipic acid for the prepara-
tion of nylon 6,6.426
Electrochemistry427 can be used to regenerate an expen-
sive or toxic reagent in situ. An example is the electrical re-
generation of periodate that is used for the oxidation of vici-
nal diols such as sugars. When used with osmium oxidations,
it can keep the level of the toxic metal reagent quite low. In
Chap. 4, an example of the conversion of a naphthoquinone
to its epoxide by electrolysis of aqueous sodium iodide was
given. The sodium hydroxide and iodine produced by elec-
trolysis react to form hypoiodite that adds to the double bond
to form the hydroxyiodide, which then eliminates sodium io-
dide by the action of the sodium hydroxide to re-form the
sodium iodide.428 Electricity can be used in oxidations and
15.8
15.9
463
reductions instead of reagents. When iodine is reduced to hy-
driodic acid in this way, no waste products are formed.429
Phosphorus-containing wastes are produced in the conven-
tional process using phosphorus. The new process is also
cheaper. Ketones can be converted to alcohols in up to 98%
yield by electrocatalytic hydrogenation using rhodium-mod-
ified electrodes.430 There is no catalyst to be separated at the
end of the reaction. The electrochemical hydrogenation of
water-immiscible olefins and acetylenes is enhanced by con-
current ultrasonication.431 Hydrogenation of edible oils us-
ing a cell with a Nafion membrane with a ruthenium anode
on one side and a platinum or palladium black cathode on the
other produced less of the undesirable trans-isomers than
conventional hydrogenations.432
An oxidation using a nickel hydroxide electrode is
shown in 15.8.433 Electrochemistry is also a way to produce
radicals and anions. The hydrodimerization of acrylonitrile
to adiponitrile just mentioned may involve the coupling of
free radicals. The coupling of carbonyl compounds, such as
p-tolualdehyde, to form pinacols with up to 100% selectiv-
ity, by way of free radicals, can be done electrically.434 An-
ions can also be formed electrochemically and used in situ,
as in example (15.9).435
464
15.10
Electrochemistry can also be used in a variety of other
“clean technologies,” including separations by electrodial-
ysis, recovery of metal ions from waste streams, and de-
struction of cyanide ion and organic compounds in waste
streams.436
B. Light
Light is environmentally benign, leaving no residues to be
removed in the workup of a reaction. It can catalyze some
reactions that are difficult or impossible to run in other
ways (e.g., some cycloadditions).437 Most photochemistry
is carried out using light with shorter wavelengths than
those found in sunlight. The challenge is to use sunlight as
is, or when concentrated. The degree of concentration can
vary with the optical system. The large concentration ob-
tained with solar furnaces has been suggested for isomer-
ization, cycloadditions, catalytic cyclizations, and purifica-
tion of water.438
A few examples will be given to illustrate current trends
in research. Dithianes, benzyl ethers, and related com-
pounds have been cleaved by the use of visible light with a
dye (15.10).439 (To use more of the light, mixtures of dyes
can be used.)
Benzonitrile in methanolic potassium hydroxide can be
hydrolyzed to benzamide in 96% yield using an oxophos-
phoporphyrin catalyst with 420-nm light at 20°C.440 A
combination of visible light and water was used in a cy-
clization (15.11) to produce substituted pyridines with al-
most no by-products.441
15.11
Chapter 15
Oxidation of hydrocarbons in zeolites with blue light
gives improved selectivity.442 Isobutane can be converted
to tert-butylhydroperoxide with 98% selectivity. Benzalde-
hyde is produced from toluene, acrolein from propylene,
and acetone from propane.
Photoredox reactions can be carried out with semicon-
ductors. Irradiation of nitrobenzene in the presence of zinc
oxide particles in alcohol produced phenylhydroxylamine
in 73% yield.443 Irradiation of 4-cyanophenylazide in
ethanol containing titanium dioxide gave 4-cyanoaniline in
98% yield. Photooxidation of cyclohexane in the presence
of titanium dioxide gave 85.4% cyclohexanone, 2.6% cy-
clohexanol, and 12% carbon dioxide.444 To be of use com-
mercially as part of a route to nylon 6,6, the amount of car-
bon dioxide must be reduced. This method has also been
studied for the detoxification of wastewater containing or-
ganic contaminants, such as trichloroethylene.445
Acylhydroquinones can be produced from 1,4-benzo-
quinone and an aldehyde (15.12) with light from a sun-
lamp.446 In contrast to the usual acylation with an acyl
chloride, this process produces no by-product salts.
C. Ultrasound
Many applications of ultrasound447 to the synthesis of or-
ganic compounds have been given in earlier chapters. This
technique is especially useful when a solid in a liquid has
to react. This may be a matter of the surface being cleaned
continuously by the cavitation. (Cavitation produces high
Energy and the Environment
15.12
temperatures and pressures for very short times.) It can
help when there are two immiscible liquids. In this case
mechanical stirring for macromixing may be combined
with ultrasound for micromixing. The instantaneous high
pressures obtained can be used to accelerate some reactions
when the products occupy a smaller volume than the start-
ing materials (e.g., the Diels–Alder reaction).
The cost of the ultrasonic energy needed for these mix-
ing and cleaning processes in reactions is not high because
only relatively small amounts of energy are needed. In con-
trast, the energy needed for doing chemistry with ultrasound
is much higher (e.g., generating hydroxyl radical in water).
If the hydroxyl radical is to be used to initiate a polymeriza-
tion, only a little may be needed, so that it may not cost too
much. The cost is still not prohibitive for reactions such as
lowering the molecular weight of polymers, if relative few
chain scissions are needed. A couple of examples from the
field of polymers will illustrate some of what can be done.
Block copolymers of polyethylene and acrylamide have
been made by ultrasonic cleavage of the polyethylene in the
presence of acrylamide.448 Maleic anhydride grafted to
polypropylene in 93% yield when the two were ultrasoni-
cated at 60°C in the presence of benzoyl peroxide.449
Ultrasound can be scaled up to large volumes in batch or
continuous flow systems. It can also be combined with an
extruder, where it speeds up extrusion and allows the pro-
cessing of polymers of higher molecular weight that may
have improved tensile strength. It is a technique that de-
serves to be used more often, for it can often save money
by reducing reaction times.
D. Microwaves
As illustrated by examples in earlier chapters, the use of
microwave energy,450 instead of conventional heating, of-
ten results in good yields in very short times. (Ovens with
homogeneous fields of focused microwaves, if temperature
control and power modulation are present, can lead to im-
465
proved yields compared with conventional ovens.) There
must be something present that absorbs the microwaves.
In the synthesis of zeolites, it is necessary to hold the gel
at elevated temperatures for extended time periods to in-
duce the zeolite to crystallize. Zeolites can be made from
fly ash in 30 min when microwaves are used, compared
with 24–48 h when the mixture is just heated.451 In the syn-
thesis of zeolite MCM-41, heating for 80 min at 150°C is
replaced by the use of microwaves for 1 min at 160°C.452
Varma and co-workers have run many organic reactions
with clay catalysts without solvent in open vessels for 1–3
min to obtain good yields of products.453 These include the
preparation of imines and enamines from ketones and
amines in 95–98% yields, oxidation of alcohols to ketones
with iron(III) nitrate on clay, cleavage of thioketals, and
others. That these yields cannot be obtained in a compara-
ble period of simple heating make these workers feel that
there is a special microwave effect. It is possible that the ef-
fect is due to instantaneous high temperatures at the surface
of the solid. It may also be that microwaves facilitate con-
tact between the solid and liquid reagents. If so, a combi-
nation of ultrasound and microwaves might be even better
for reactions that take somewhat longer to run with mi-
crowaves than those just cited. While the debate about the
special microwave effect is still going on, it appears to have
been settled for at least this one class of reactions.
The application of microwave energy as an alternative
to conventional heating needs to be tried wherever mi-
crowave-absorbing (i.e., polar materials) are present. These
include not only inorganic compounds, but also water, al-
cohols, amides, and many other oxygen-containing com-
pounds, but not hydrocarbons, such as hexane and toluene.
Xylene can be heated with microwaves by dispersing 1–2%
of cobalt or magnetite, 5- to 20-nm nanoparticles, in it.454
A magnet is used to recover these for reuse in the next run.
Microwaves enhance the solid-state polymerization of
polyethylene terephthalate at 236°C and nylon at
182–226°C by enhancing the diffusion of small
466
molecules.455 There is considerable current enhancement
when microwaves are used with platinum microelec-
trodes.456 Microwaves have been used with metal powders
at high temperatures to produce parts that are superior to
those made by the usual sintering in powder metallurgy.457
They have also been used in the production of ceramics.458
Regeneration of zeolites that had been used to trap volatile
organic compounds with microwaves, required only one-
third as much energy as conventional heating.459
Microwaves should be well suited for continuous tubu-
lar reactors, where they might reduce the amount of energy
needed, reduce costs, and increase the output of a plant. If
water were inert, it might be used to absorb the microwave
radiation, the reagents being in solution or in an emulsion.
Further research will undoubtedly find many more applica-
tions for this technique.
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(g) T.J. Mason, ed., Advances in Sonochemistry, J.A.I.
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J.–C. Bolomey, Microwave Processing of Materials V,
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461. Worms or single cell protein for feeding back to the ani-
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RECOMMENDED READING
1. J. Kaiser, Science, 1997; 278:217 [global warming].
2. Union of Concerned Scientists, Assessing the Hidden Costs
of Fossil Fuels, Cambridge, MA, Jan. 1993.
3. L. Starke, ed., State of the World 1995, W. W. Norton, New
York, 1995, pp. 58–75 [energy from sun and wind]; 95–112
[better buildings].
Energy and the Environment
4. Union of Concerned Scientists, Putting Renewable Energy to
Work in Buildings, Cambridge, MA, Jan. 1993.
5. M. Brower, Environmental Impacts of Renewable Energy
Technologies, Union of Concerned Scientists, Cambridge,
MA, Aug. 1992.
6. K. Voss, A. Goetzberger, G. Bopp, A. Haberle, A. Heinzel,
and H. Lehmberg, Sol. Energy, 1996; 58:17. [self-sufficient
solar house in Freiburg, Germany].
7. J.E. Ludman, J. Riccobono, I.V. Semenova, N.O. Reinhand,
W. Tai, X. Lo, G. Syphers, E. Rallis, G. Sliker, and J. Martin,
Sol. Energy, 1997; 60:1 [holographic system for photovoltaic
cells]
8. W. Wettling, Sol. Energy Mater. Sol. Cells, 1995; 38:494.
[efficient photovoltaic cells from crystalline silicon].
9. J. A. Turner, Science, 1999; 285:687.
EXERCISES
1. Keep track of the single-use throwaway items that
you use for a week. What reusuable items could be
used instead?
2. Monitor the cars on a road during rush hour to see
how many cars have more than one person in them.
Also count walkers and bikers.
3. See if you can find the following in your area:
Passive solar heating and cooling
Active solar eating
Photovoltaic cells
Windmill
A greenway
479
Use of biogas from a landfill
District heating
An electric car
When you find them, see if the owner or operator
will be willing to share operating data with you.
4. Devise a system of incentives and disincentives to
help solve the problem of global warming in your
area.
5. Hydrogen can be stored by hydrogenating benzene
to cyclohexane, the recovered later by dehydro-
genation. Benzene is a carcinogen. Figure out a bet-
ter chemical way to store hydrogen that does not in-
volve a carcinogen.
6. Light energy can be stored by converting norborna-
dienes to quadricyclanes, and the energy released
later by reversing the reaction. A cheaper, better
way is needed that has a high-energy density and
that is reversible over a great many cycles. Can you
devise one?
7. Waste heat might be recovered for use later at the
same or a different location by conversion of one
chemical compound to another. Can you figure out
a system that will do this with minimal losses over
many cycles. The chemical should be abundant,
cheap and, preferably, suitable for transport through
a pipeline. It will be even better if the system can
store excess summer heat for use in the winter. (Na-
ture does this by converting carbon dioxide in the
air to wood in trees.)
16
Population and the Environment
I. THE PROBLEMS
Aging farmers often divide their farmland among their
children. This is not a problem if there are no more than two
children. However, many farm families have many chil-
dren to help in the work on the farm. In this case, the chil-
dren will each have less land than the parents. If this is done
over a few generations, the final farm size may not be
enough to provide sufficient food for the family.1 Sociolo-
gists studied this problem in the Rio Grande Valley in New
Mexico in the 1930s. Rwanda affords a more recent illus-
tration. The population grew from 2.5 to 8.8 million from
1950 to 1994 as the average woman had eight children, the
highest rate in the world.2 The nation had the highest pop-
ulation density in Africa. The average family was trying to
support itself on only 0.7 ha in the 1990s.3 This may have
been one of the reasons for the bitter civil war that erupted
in that nation.
There are various responses to this shortage of land. One
is to move ever higher on the mountainside and cut down
the forest so that crops can be raised causing severe ero-
sion. Such farmland does not last very long, so that it is
necessary to move fairly often and repeat the process.
Some live in flood-prone areas because they have no other
place to live, as in Bangladesh. The floods become worse
as other farmers in mountains upstream cut down more for-
est to make cropland. Another system is to send the hus-
band to work in another country to earn money to support
the family. This leaves the wife to look after the children,
farm the fields, gather the firewood, get the water, and all
the other chores. In many places in the developing world,
firewood and water are in short supply, so that longer and
longer trips are needed to obtain them. This is one reason
for deforestation. Many families, unable to obtain more
land, move to the cities in search of jobs. Here, they may
481
live in shantytowns lacking adequate water, sanitation, and
other services. They may do menial jobs or be unemployed.
The number of urban poor in Latin America was 44 million
in 1970. In 1990, the number had reached 115 million.4
The nutrients in the tropical forests are largely in the
vegetation. Slash and burn agriculture is one way of ob-
taining them. The forest is cut down and burned to release
the nutrients, which are then available to grow crops. After
a few years, this system is depleted and the family moves
on to repeat the process in another location. It takes an ex-
tended time period for the land to become forest again and
recover. If there are too many people doing this, the whole
forest can be depleted and destroyed. In some countries, ef-
forts have been made to resettle surplus population by
clearing tropical forests. The soils are fragile and remain
fertile for only a few years. This has been true in parts of
Brazil. In some parts of this country, soils treated in this
way undergo an irreversible change in structure, a harden-
ing, that prevents any future use. These changes can occur
in land used to graze cattle as well as on land used for row
crops.
The overall effects of these processes can lead to deser-
tification, deforestation; increased flooding, less water in
the ground and in rivers; depletion of underground
aquifers;5 loss of biodiversity; loss of topsoil; more dis-
ease,6 famine, and unemployment; as well as political in-
stability.7 The world has undergone a population explo-
sion, with the time to add each new billion becoming
shorter (Table 16.1).8
Even though fertility is declining (down from six chil-
dren per woman to three in the developing world), it is still
above the replacement level of 2.1.9 Seventy countries
(largely in the developed world) have achieved stable or
negative growth.10 In the developing world where 98% of
future growth is expected to occur,11 most countries have
482 Chapter 16

Table 16.1 Population Growth Over Time Greece (1.4), Austria (1.5), Bulgaria (1.5), Slovenia (1.5),
and Romania (1.5).17
Date Population (in billions)
Various proposals have been made for ways to combat
1830 1 these problems. One is to resettle surplus population in new
1930 2 lands. The problem is that most of the suitable land is al-
1960 3 ready occupied. Efforts to put people into the rain forests of
1974 4 Brazil and Indonesia have not worked well. The land was
1987 5 not very suitable for conventional farming. Migration to
1999 6 other countries has been used as a safety valve in the past,
as in the case of Ireland. There is an ethical question over
whether it is right to expect a nation that has kept its popu-
not reached this level. There is also a large population mo- lation growth rate under control to absorb the surplus from
mentum effect as large numbers of persons reach repro- ones that have not.
ductive age. In most countries in Africa, 45% of the people Plant breeders carried out a “green revolution” by pro-
are younger than the age of 15. ducing more productive varieties of wheat, rice, and other
Of the world’s 6 billion people, 1.3 billion live in abso- crops. These varieties required more water or fertilizer,
lute poverty. Approximately 30% of the world’s labor force which some of the very poor could not afford. In addition,
of 2.8 billion people are either unemployed or underem- they decreased the genetic base of these crops, perhaps
ployed (i.e., not earning enough to lift themselves and their eliminating some less productive varieties that are more
families out of poverty).12 At the present rate of population tolerant of drought, poor soil, and disease. From the fore-
growth, 1 billion new jobs will be needed by the year 2005. going figures, it can be seen that another green revolution
Roughly, 1 billion people go to bed hungry each night.13 is needed if the food supply is to keep up with the number
There are food shortages in 86 countries. Africa produced of people. With current technology, it is not clear how this
30% less food per capita in 1998 than it did in 1967.14 Half might be accomplished.18 Breeding plants that will produce
the children younger than the age of 5 in Guatemala are un- food in drier soils and in more saline soils, or that could be
dernourished.15 In Mali, 23% of the children are too thin. irrigated by seawater, is being studied. A genetically engi-
More than 1.5 billion do not have clean drinking water or neered Arabidopsis thaliana was able to grow in 0.2-M
sanitation. Women have a disproportionate share of the sodium chloride.19 Further work is needed to apply this
problems. They represent 66% of illiterates and 70% of the method to crop plants. We now live in a human-dominated
world’s poor. The world’s poorest country is Mozambique, landscape, where one-third to one-half of the earth’s sur-
with a gross national product (GNP) per capita in 1993 of 80 face has been transformed and where over half of the ac-
dollars.16 Its population of 16 million is growing at the rate cessible freshwater has been put to use.20 This makes it dif-
of 2.7%/yr. At this rate, the population will double in 26 ficult to develop new irrigated lands. The loss of
years. Ethiopia, with an annual GNP per capita of 100 dol- agricultural land to urban sprawl each year will make it that
lars will see its population double in 22 years. (This is the much more difficult to produce enough food to feed every-
country where a major famine a few years ago required in- one adequately. Sixty-six percent of the world’s marine
ternational help.) Tanzania with a GNP per capita per year fisheries are either fully exploited or overexploited. Africa
of 100 dollars will double its population in 21 years. In con- now needs 14 million tons more grain annually than it
trast, the figure for the world’s richest country, Switzerland, produces.21
is 36,400 dollars. It is followed in descending order by Lux- There are food surpluses in Europe and the United
embourg, Japan, Denmark, Norway, Sweden, United States, partially as a result of government subsidies. It has
States, Iceland, Germany, and Kuwait. Infant mortality is been suggested that these be used to feed hungry people in
highest in Afghanistan and Mozambique at 162:1000 live the developing world. This might be used to buy time to
births. It is lowest in Japan, Singapore, Iceland, and Sweden confront the real problem of overpopulation. There are
at 5:1000. Life expectancy is lowest in Guinea-Bissau at 39 questions on who would pay the farmers for the food, if
years and highest in Japan at 79 years. those who need it most are too poor to pay for it. There is
Among the 85 nations that believe that their birth rates also the question of whether these surpluses were produced
are too high are Zaire (6.7 children per woman), Saudi Ara- using sustainable methods (i.e., without excessive loss of
bia (6.4), Somalia (7), Cote d’Ivoire (5.7), and Syria (4.7). topsoil or depletion of underground aquifers, or saliniza-
Somalia required an international team to restore order af- tion of irrigated lands). Even with its modern food distri-
ter its government collapsed. At the other extreme are bution system, the United States still has some hungry peo-
Hong Kong (1.2), Spain (1.2), Germany (1.3), Italy (1.3), ple in it. Another suggestion to release more food for
Population and the Environment
human use is to adopt vegetarian diets. It takes about 9 lb
of food to produce 1 lb of beef. It takes only 2 lb of feed to
produce 1 lb of chicken or catfish. If people in affluent
countries ate less meat, there would be more food to feed
those who are hungry. Some meat is produced on rangeland
that is unsuitable for growing crops. It has also been sug-
gested in China that people eat the grain, rather than mak-
ing it into beer. Another suggestion is to have fewer ani-
mals as pets, so that food now being fed to pets could be
used to feed humans instead.
The United States is one of the fastest-growing nations
in the industrialized world.22 It is adding 2.4 million people
each year, one-third of whom come by immigration. (Im-
migration and births to immigrant women accounted for
70% of the increase in the population in the 1990s.23) It is
the third most heavily populated nation in the world after
China and India. Its present population is 264 million.24 Its
incidence of teenage pregnancy is much higher than in
other industrialized nations. This is twice that in England
and Canada and nine times that in Japan and the Nether-
lands.25 The affluence and overconsumption of Americans
means that the 24 million people born in the last decade
will consume more resources than the entire population of
Africa.26 America’s annual population growth causes
about as much global warming as that of China and India
combined and 2.5 times that of Africa.27 A child born in the
United States will have twice the impact of one born in
Sweden, 3 times one in Italy, 13 times one in Brazil, 35
times one in India, 140 times one in Bangladesh, and 280
times one in Nepal.28 The average person in a developed
nation uses 5 times more fertilizer, 12 times more oil, and
24 times more natural gas as his or her counterpart in a de-
veloping nation.29 He or she produces 40 times more in-
dustrial waste and 52 times more industrial effluents. The
United States leads the world in the per capita emissions of
carbon dioxide.30 The influence of the consumption in de-
veloped nations is felt beyond their borders, because they
need to import many raw materials. As an example, tropi-
cal forest in Costa Rica was cut and replaced with grass so
that cattle could be grown on it to supply America’s fast-
food restaurants with hamburger. Tropical forests have also
been cut to supply hardwoods for furniture, paneling, and
such, for use in developed nations. Many minerals used by
the United States are mined in developing nations.
How many people can the world support with present-
day technology?31 Opinions vary, but it is clear that one
cannot expect endless population growth and endless in-
creases in food production.32 It is important to support
these people in a sustainable manner that does not foreclose
any options for future generations. This means that prac-
tices that permanently damage land by loss of topsoil, nu-
trients, depletion of groundwater, or other, must be
483
stopped. The loss of biodiversity must be stopped. Our be-
havior must be changed so that no further loss of the ozone
layer occurs and global warming is moderated. It is also
clear that if the population becomes too large, the standard
of living will decline in more places than it has at present.
If the population grows to the point where the natural re-
source base can no longer support it, it may be controlled
by famine, disease, and war. A more humane way of ap-
proaching the problem is through wider use of family plan-
ning on a large scale. The rest of this chapter will deal with
possible ways to do this, as well as point out additional re-
search that needs to be done.
II. CHEMISTRY OF HUMAN
REPRODUCTION
The reproductive process is controlled by several hor-
mones, as shown in Fig. 16.1.33 The biological effects and
the interactions of the hormones in the female are shown on
the left and those in the male on the right.
The hypothalamus produces gonadotropin-releasing
hormone (LHRH or GnRH), which stimulates the pituitary
gland to produce follicle-stimulating hormone (FSH), and
luteinizing hormone (LH). LHRH is a decapeptide. FSH
and LH are heterodimeric glycoproteins (with - and -
subunits) with molecular weights of 34 and 28.5 kDa, re-
spectively. FSH and LH stimulate an oocyte (an immature
ovum) to develop. (The female is born with all the oocytes
that she will ever have.) At the same time, the ovarian fol-
licles synthesize the estrogen, estradiol, the biosynthesis
starting from cholesterol (16.1). Small amounts are also
made elsewhere. Estrone and estriol are active metabolites
of estradiol. (Note that these estrogens have an aromatic A
ring so that they are phenols.)
One ovum matures in the follicle in each 28-day cycle.
At the same time, the endometrium (the lining of the
uterus) proliferates to receive the ovum if it is fertilized.
During the middle and late portions of this follicular
phase, the concentration of FSH falls and the concentra-
tion of LH rises (in response to an increasing level of es-
trogen). This triggers ovulation by rupture of the follicle
at about the 14th day. The follicle then becomes the cor-
pus luteum, which produces progesterone. The estrogen
and progesterone inhibit FSH and LH. The life of the cor-
pus luteum is about 14 days. If fertilization takes place,
the lifetime of the corpus luteum is extended by the action
of chorionic gonadotropin secreted by the implanting
blastocyst (which results by cell division of the fertilized
ovum). Human chorionic gonadotropin (hCG) is another
dimeric glycoprotein, with a molecular weight of 36.6
kDa. Inhibin and activin are glycoproteins that are in-
484 Chapter 16

Figure 16.1 Chemistry and control of reproduction. Reprinted from W.J. DeKoning, G.A. Walsh, A.S. Wrynn and D.R. Headon,
Biotechnol., 1994; 12:988 with permission of Nature Biotechnology and the authors.

volved in feedback loops. During pregnancy, the produc-
tion of progesterone (16.2) by the placenta is about ten
times that of the ovary. If fertilization does not occur, two
superficial layers of the endometrium are shed in men-
strual bleeding, and the cycle begins again.
In the male, the FSH and LH cause the testes to produce
androgens (male sex hormones), of which testosterone (see
16.2) is typical. (Both progesterone and testosterone are
also derived by biosynthesis from cholesterol. A microbio-
logical process for the conversion of cholesterol to testos-

16.1
Population and the Environment
16.2
terone for therapeutic use has been developed using a My-
cobacterium.34) Sperm are infertile when they leave the
testis. They mature in their 2-week trip through the epi-
didymis, which leads to the vas deferens and the penis.
The use of androstenedione (16.3), as a metabolic pre-
cursor of testosterone, to increase athletic prowess is un-
proved and may lead to detrimental effects, such as ele-
vated blood lipid levels, liver problems, and testicular
atrophy.35
III. THE CHEMISTRY OF FAMILY
PLANNING
In the United States, 60% of pregnancies are unintended.36
Unwanted children often receive less, or less caring, atten-
tion and can become social problems. A World Fertility
Survey indicated that 500 million women do not want any
more children, did not want their last child, or want to con-
trol their fertility, but lack access to the necessary family-
planning knowledge or services.37 Thus, there is a major
need for better application of the methods known to be ef-
fective today, as well as research to lead to newer, and pos-
sibly cheaper, methods with fewer side effects. Two re-
views give good coverage of the subject.38
16.3
485
In theory, a knowledge of the woman’s menstrual cycle
might allow a couple to restrict intercourse to periods
where fertilization would not occur. In practice, the method
is unreliable. The time of ovulation can vary from month to
month. The ovum must be fertilized within 12–24 h after
ovulation. However, sperm can remain viable in the female
reproductive tract for 5–7 days and possibly more. Other
more reliable methods must be considered.39 It is important
to remember that almost all drugs have side effects, which
may be minor in most persons, but may be major in some.
Thus, any method that is used must have minimal side ef-
fects. Doctors select among the different methods to
achieve the best one for any given individual.
A. The Use of Sex Hormones
Progestins can be used alone as oral contraceptives,40 but
they are less effective and have more side effects, such as
intermenstrual or breakthrough bleeding and spotting, than
when used in combination with estrogens. These inhibit
ovulation by negative feedback on the hypothalamus and
the pituitary gland, which decreases secretion of FSH and
LH. Newer oral contraceptives use a quarter of the estrogen
and one-tenth the progestin used in former years.41 They
often vary the amounts and proportions of estrogen and
progestin through the phases of the menstrual cycle to min-
imize the amounts needed and the side effects. For this pur-
pose, the natural estrogens and progestins would have to be
used in large amounts, because they are not absorbed well
from the gastrointestinal tract and remain active for only a
short time. Synthetic analogues have overcome these draw-
backs, so that only 30–35 g of estrogen and 0.15–1.00 mg
progestin need be used. Two typical ones are shown in
16.4.
The methyl ether of ethinyl estradiol (a monoether of the
phenol group) can also be used as the ether is cleaved in the
body. A variety of synthetic progestins are used.
486
16.4
The health benefits of oral contraceptives go beyond
contraception and outlast the reproductive years.41 These
include reduced incidence of ovarian and endometrial can-
cers. Oral contraceptives do not increase the risk of breast
cancer, heart disease, or blood clots.42
Long-acting injectable analogues of the sex hormones
(16.5) are also used. Depo Provera is injected every 3
months as a microcrystalline aqueous suspension. The ac-
tive compound, medroxyprogesterone acetate, dissolves
slowly as needed. Another compound that is injected once
a month is an ester that probably hydrolyzes slowly.
Implantation of analogues of the sex hormones in slow-
release formulations can offer protection for 5 years. Nor-
plant consists of six match-like cylinders of levonorgestrel
(see 16.4) in a silastic matrix (made from a copolymer con-
taining dimethylsiloxane and methylvinylsiloxane units).
The implant can be removed surgically at any time that the
woman no longer desires protection. Occasionally, there
have been problems with the removal. For this reason,
slow-release formulations of levonorgestrel in biodegrad-
able polymers, such as poly(caprolactone) are being stud-
ied. The effective life is expected to be 12 months. There is
16.5
Chapter 16
a problem if the woman wants it removed surgically in a
shorter time during which the polymer may have degraded
appreciably.
Contraceptive vaginal rings have been made that release
the steroid slowly. (The walls of the vagina are easily pen-
etrated by the hormones.) This can allow the use of drugs
that have low oral activity. For example, an estrogen–pro-
gestin mixture can be incorporated in a silastic matrix. The
ring has the advantage that it can be removed at any time
without surgery.
B. Intrauterine Devices
Intrauterine devices (IUDs) can also contain the steroids.
One style contains 38 mg of progesterone, which is re-
leased slowly over 1 year. One containing levonorgestrel is
under development. Unmedicated rings appear to work just
as effectively, although the details of their action are not
well known. They appear to create an environment unsuit-
able for sperm and ovum and inhibit implantation. They
can be made of polyethylene, stainless steel, or copper,
with the last being the most common.
Population and the Environment
C. Morning-After Treatments and
Abortifacients
The chance of pregnancy can be reduced by 75% by a high
dose of oral contraceptives taken within 72 h (under a doc-
tor’s supervision) after unprotected intercourse.43 This usu-
ally consists of taking one set of pills followed by a second
set 12 h later. The use of a product containing only lev-
onorgestrel has cut the side effect of nausea by over 50%.44
Additional work is needed to improve the efficacy and to
reduce the side effect of nausea further. Inclusion of an
antinausea drug may help. Danazol (16.6) may be the an-
swer. It is said to be highly effective with few side effects.
The antiprogestin, mifepristone (RU-486; see 16.6), can
be used in conjunction with a prostaglandin as a morning-
after pill.45 It induced menstruation in 98% of women who
were up to 10 days late with their periods. Mifepristone can
also be used to terminate pregnancy in the first trimester in
a nonsurgical abortion.46 When the mifepristone is fol-
lowed with a prostaglandin, such as misoprostol (16.7),
given orally 36–48 h later, the abortion rate is greater than
95%. It is approved for use until up to 49 days of pregnancy
in France and China, and for up to 63 days in Sweden and
the United Kingdom. More than 200,000 women in France
and the United Kingdom have used this method. Tests have
also been run with 2100 women in 17 clinics in the United
States.47 There were no side effects in 98% of the cases in
the United States.48 Mifepristone was approved for use in
the United States in September, 2000. Mifepristone is also
being studied for treatment of Cushing’s syndrome (caused
by overactive adrenal glands), infertility, breast cancer, en-
dometriosis, uterine fibroid tumors, brain tumors, and for
the management of labor at the end of a normal pregnancy.
16.6
487
Mifepristone binds to the receptor that normally binds
progesterone, preventing transcription of the genes normally
triggered by progesterone. Other routes by which abortifa-
cients may work include inhibition of progesterone biosyn-
thesis, increased metabolism of progesterone, and inhibition
of the chorionic gonadotropin that supports the corpus lu-
teum. Prostaglandins serve many functions in the body, in-
cluding a role in childbirth.49 The body makes them from
arachidonic acid (16.7), which is obtained from the diet or is
made, in turn, from linoleic acid, an essential fatty acid.
A combination of two prescription drugs, misoprostol
(used for treatment of gastric ulcers; see 16.7), and
methotrexate (used for cancer, arthritis, and psoriasis; 16.8)
can also be used to terminate pregnancy. Of 178 women in
the early weeks of pregnancy receiving this treatment, 171
terminated. More than 650 women have now used this
method with good results50. In countries without access to
mifepristone, each drug has also been used alone for med-
ical abortions.51
The isocupressic acid (16.9) in the needles of Pinus pon-
derosa can cause abortions in cattle that eat the needles.52
This may be a possible lead for new abortifacients for
humans.
D. Physical Barriers
The physical barriers include diaphragms and cervical caps
made of rubber that fit in the vagina over the cervix. They
are mechanical barriers to block the passage of sperm and
are often used with spermicidal agents, such as nonoxynol
(a surfactant; 16.10).
These must fit well, be inserted correctly, and remain in
place long enough for the spermicide to act. A vaginal
488 Chapter 16

16.7

16.8

16.9

16.10
Population and the Environment
sponge is less effective. India is testing oil from the neem
tree (Azadirachta indica), with and without other plant ex-
tracts, as a vaginal cream or suppository for contracep-
tion.53 (This is the tree that produces the insect repellent
discussed in Chap. 11.) One problem that must be over-
come is the sharp unpleasant odor of the oil.
The condom is the only method of contraception that
prevents the transmission of disease at the same time. Sex-
ually transmitted diseases include those caused by Chlamy-
dia trachomatis, Neisseria gonorrhoeae, Trichomonas
vaginalis, Treponema pallidum, herpes simplex virus II, hu-
man papilloma virus, and human immunodeficiency virus
(HIV). Chlamydia I infection is the most prevalent sexually
transmitted disease in the United States, with up to 4 million
cases per year. It can cause pelvic inflammatory disease,
tubular pregnancies, and infertility in women. It responds to
treatment with antibiotics.54 Its complete genome has been
sequenced. (Gonorrhea is caused by Neisseria and syphilis
by Treponema. The United States has the highest rate of
sexually transmitted diseases in the industrialized world.)
Although it may be possible to develop vaccines for these in
the future, almost none is available today.55 Genital herpes
has been prevented by controlled release of antibodies from
poly(ethylene-co-vinyl acetate) disks.56
Condoms work well if they are of good quality, are not
too old, and stay on. They must be used with water or gly-
col-based lubricants, for petroleum-based lubricants cause
them to lose strength and possibly fail. Condoms are made
by dipping a form coated with a coagulant into a latex of
natural rubber. After drying, a second dip is done. The
problem is that there are flaws in many of the condoms.
About 10–15% of the rubber used in making condoms and
rubber latex gloves is wasted in rejects.57 The usual testing
does not detect holes smaller than 10 m.58 The problem is
that the 5-m holes that are present are large enough to al-
low the human immunodeficiency virus to pass through.
The virus particles have a diameter of 0.1 m, compared
with 6.0 m for the bacteria causing syphilis and 45 m for
the sperm. Hepatitis B virus is about 20 nm in size. Use of
a condom reduces the chance of transmitting HIV tenfold,
but not to zero. Newer testing methods using high-voltage
electricity can decrease the measurable size to 1 m or
less.59 These are said to find the small holes through which
the viruses could pass. Condom quality improved in the 4
years up to 1999.60 The Johns Hopkins School of Public
Health reports that that HIV cannot penetrate an intact la-
tex condom.61 (In 1998 there were 33 million cases of ac-
quired immune deficiency syndrome (AIDS) in the world,
including 5.8 million new cases that year.62)
There is a need for vaginal creams that are not only sper-
micidal, but which also inactivate bacteria and viruses.
Among those being developed is an emulsion of oil, water,
489
and two common laboratory detergents that kills fungi,
bacteria, viruses, sperm, and red blood cells, but no other
animal cells.63 Another is a cellulose ether quaternary am-
monium salt that coats mucosa of the reproductive tract and
slows down the sperm.64 It is used with dextran sulfate, a
known virucide, and a surfactant that dissolves the outer
shell of the sperm.
Another problem is that some persons are allergic to the
proteins often found in natural rubber. This can be avoided
by the use of a polyurethane condom. Unfortunately, as
now made, these are more likely to tear (7–9% of the time)
than the rubber latex condoms (2% of the time).65 It has
been suggested that they be made of guayule rubber latex,
which is free of the allergens.66 Thermoplastic elastomers,
such as polystyrene-b-(ethylene-co-butene)-b-polystyr ene
have been used to make gloves that are more resistant to
ozone than those made of natural rubber.67 These should
resist aging better than those made of natural rubber. It
should be possible to mold a condom without holes from a
thermoplastic rubber.
E. Contraceptives for Males
Additional contraceptives for males are being developed to
supplement the condom. A study in Minnesota has shown
that birth rates correlate with sperm count in the range of
46.5–123 million/mL.68 Weekly injections of testosterone
in 399 men reduced the sperm count for 98.6% of them.69
A sperm count of 3 million or fewer almost guaranteed no
conception. Only four pregnancies occurred in the trial.
The testosterone can also be administered by skin patches,
a method more convenient than injections.70 A combina-
tion of a skin patch of testosterone and a progesterone pill
reduced men’s sperm counts to zero.71 When the treatment
was discontinued, the sperm counts gradually returned to
normal. A male contraceptive pill containing testosterone
and desogestrel was 100% effective in clinical trials with
no side effects.99 The Population Council and Sano are
working with a synthetic androgen that is ten times as ac-
tive as testosterone. It maintains normal sexual functions
and muscle mass without overstimulating growth of the
prostate gland. Organon is testing an androgen that is taken
orally in pill form.72 Indenopyridines, which disrupt the de-
velopment of sperm, are being tested by the Research Tri-
angle Institute in North Carolina.73 Any method that relies
on inhibiting spermatogenesis may require 2–3 months to
become effective. This time is needed for normal sperm
originally present to pass through and be eliminated from
the system. Spermatogenesis is controlled by FSH and LH.
It may be possible to inhibit them, but testosterone supple-
ments may have to be given at the same time to maintain
libido.
490
16.11
Some male contraceptives tested in the past have been
too toxic or have not been reversible when the substance
was no longer administered or have interfered with libido.
Gossypol (16.11) from cottonseed was used in China, but
was found to have the first two problems.
Extracts of the Chinese vine, Tripterygium wilfordii,
have also shown some promise. This male contraceptive
affects sperm maturation in the epididymis. Two other
drugs work by another mechanism. They prevent the
contractions of the muscles that run along the vas deferens,
so that seminal fluid and sperm are not pushed along. This
results in a “dry” orgasm with no ejaculation. The drugs
are phenoxybenzamine (16.12), which is normally used to
control hypertension, and thioridazine (see 16.12), which
is an antipsychotic.74 The lack of ejaculation was discov-
ered as a side effect of the normal uses of the drugs.
16.12
Chapter 16
F. Sterilization
Surgical sterilization is a widely used method of contra-
ception for both men and women. The problem is that it is
very difficult to reverse if a couple wants to have more chil-
dren, as when a child dies. It may also be too expensive for
very poor women in developing countries. A newer non-
surgical approach sterilizes a woman by insertion of
quinacrine (16.13) into the uterus by a trained paramedic.75
It produces scar tissue in the fallopian tubes that prevents
pregnancy. This drug has been used over a long time period
as an antimalarial. The cost of the treatment is estimated at
less than 1.00–2.50 dollars compared with 12 dollars for
laparoscopic sterilization (45 dollars if the cost of the
whole team is included). Vasectomy for men is already
inexpensive.
Population and the Environment 491

16.13

A nonsurgical vasectomy has been investigated in India. A 13-amino–acid polypeptide that mimicks the binding re-
A styrene–maleic anhydride copolymer was injected into the gion of fertilin in step 2 inhibited fertilization in in vitro
vas deferens to block the duct.76 If removal is desired later, trials.
the polymer can be dissolved out with dimethysulfoxide. Efforts have been made to develop vaccines that will
Reversible vas occlusion has been administered successfully prevent pregnancy. Ideally, these would target some anti-
to over 300,000 males. It involves no surgery, is reversible gen that is associated only with the male (e.g., the enzymes
and costs less than $5.00 in developing countries. present in the head of the sperm that hydrolyze part of the
zona pellucida, a glycoprotein coating, that the sperm must
G. Newer Methods Under Study penetrate to reach the ovum). Sperm membrane proteins
might also be suitable antigens.79 Vaccines have also been
The relative effectiveness of the various methods is given made to hCG, which is essential for implantation of the
by the approximate numbers in Table 16.2.77 blastocyst. A subunit of this protein was attached to a dis-
A thorough knowledge of the process of human repro- abled toxoid as a carrier to make the antigen. Vaccines for
duction may lead to other approaches. The gamete recog- males have been directed toward antibodies that neutralize
nition proteins in sperm–egg interactions in animals are gonadotropin-releasing hormone, which is needed for the
just beginning to be understood.78 The process involves production of sperm. Although the vaccines work, they
five steps: only last a few months, so that booster shots are required.
1. Molecules released by the egg attract the sperm. Another approach is to find compounds that block the
2. The protein integrin on the egg binds to a to a small enzymes that allow the sperm to make a hole through the
piece of the sperm protein fertilin. zona pellucida.80 One product that does this was 92% ef-
3. The acrosomal vesicle on the head of the sperm fective in preventing pregnancy in rats, indicating a need
opens. for further optimization. It is possible that combinatorial
4. A protease creates a hole in the egg envelope for the synthesis of polypeptides can lead to compounds that will
sperm to pass. competitively block the FSH, LH, and hCG at their recep-
5. The two cells fuse. tor sites. Recombinant analogues of FSH, LH, hCG, and
LHRH are being reported.81 Some of these might be useful
in contraception. Others might be useful in treating infer-
Table 16.2 Effectiveness of Various Contraceptive tility and other reproductive deficiencies. Each stage in hu-
Method man reproduction needs further study to see if synthetic
Method % Pregnant in 1 yr analogues of the natural compounds can block the recep-
tors or otherwise disrupt the process without undesirable
Rhythm method 8.5 side effects.
Spermicides 7
Female condom 5
Male condom 2 IV. SUMMARY OF THE PROBLEM
Oral contraceptive 1
Sterilization 0.5
Relatively few drug companies carry out research on con-
Norplant 0.3
traception. Not one of the eight largest pharmaceutical
492
companies in the world is doing contraceptive research and
development.82 Most companies are concerned about po-
tential liability, poor profits, and high development costs.83
Vaccine research boomed after a 1986 U. S. law shielded
vaccine makers from liability.84 The committee of the U. S.
Institute of Medicine investigating the problem recom-
mends that U. S. product liability law be reformed, that
health insurance cover contraceptives, and that interna-
tional health agencies pool their funds to create a large mar-
ket. Many of the poor people of the world cannot afford to
pay for the contraceptives. Over a 5-year period an Ameri-
can woman may spend 1784 dollars for oral contraceptives,
or 1290 dollars for Depo Provera, or 850 dollars for Nor-
plant.85 A woman in a developing nation may obtain these
for a much lower price if they are supplied by an interna-
tional health agency. There is a campaign for contraceptive
equity in the United States. Health insurance that covers
Viagra, a drug for male impotence, should also cover con-
traceptives for women, but it often does not.
Even though the poor may not be able to afford to pay
for family-planning services, it is important to provide
them. In the United States, every public dollar spent on
such services saves the taxpayers almost $4.50.86 On the
international scene, it will be cheaper to subsidize the dis-
tribution of family-planning services than to provide
famine relief, refugee camps, money for defense, military
intervention, and so on. Less than 1% of development aid
goes to family planning. The United States ranks last
among 21 industrialized nations in development aid to
other countries (as a percentage of gross national product).
It spends 0.10%, compared with the 0.97% of Denmark,
the highest in the list.87
The state of Kerala in southern India has shown how to
control population growth, even though it is not wealthy.88
Its per capita income ($300/yr) is 1/65 that of the United
States. Its population of 30 million people lives in land
about the size of Vancouver Island, British Columbia. Life
expectancy is high. Infant mortality is low. The birth rate is
lower, and the literacy rate higher, than in the United
States. The state spends 60% of its budget on health and ed-
ucation. Women and men are treated equally under this
system. It may also have old-age pensions. The secret to the
control of population in developing nations appears to be to
improve the social status of women and to focus on the sat-
isfaction of basic human needs.89
Pakistan has been at the other extreme in government
expenditures. In 1990, it spent more than twice as much on
the military as on health and education combined. 90 Its
population is now 146 million. At the current fertility rate
of 5.8 children per woman, the population will double in 25
years. The Pakistani Minister of Population Welfare visited
Washington, DC in 1997 to ask for financial aid to deal
Chapter 16
with this problem. At the present time, 25% of the married
women in the country use contraceptives.91 The cost of
providing family planning and reproductive health services
for a year to every couple in the world that needs and wants
them has been estimated at 17 billion dollars. This is what
the world spends each week on armaments.92 This same
amount is spent for pet food in the United States and Eu-
rope each year.
Fertility declines in East Asia since 1950 have been dra-
matic, dropping to about replacement levels or below in
Japan, Taiwan, Korea, and China.93 In Thailand, fertility
dropped from 6 children per woman in the 1960s, to 3.7 in
1980, and to the replacement level of 2.1 in 1991.94 Adult
women in Thailand have a literacy rate of 90% compared
with 96% for men.
Contraceptive use varies widely among countries. The
highest use is in France and Belgium, with rates of 80 and
79%, respectively. The United States ranks tenth at 74%.
The lowest rate, 1%, is in Somalia. In Ethiopia the rate is
2%. In the poorest country in the world, Mozambique (80
dollars per capita in 1993), the use rate is 4%. Military in-
tervention was necessary to keep a government in Somalia.
Ethiopia required extensive famine relief. Postwar recon-
struction in Mozambique has required hundreds of millions
of dollars in foreign aid.95
GH Brundtland, former prime minister of Norway, said,
“Population growth is one of the most serious obstacles to
world prosperity and sustainable development.”96 The bi-
ologist Norman Myers says, “Family planning could bring
more benefits to more people at less cost than any other sin-
gle technology now available to the human race.”97 An-
other author feels that, “Population growth is just one agent
in the degradation of our environment. Unsustainable con-
sumption patterns in industrialized nations, poverty, un-
equal access to resources and the low status of women in
many parts of the world are all implicated.”98 The example
of Kerala shows how to slow population growth rates. No
one is quite sure how to reduce consumption to sustainable
levels, although this will have to be done at some point.
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45. R.F. Service, Science 1994; 266:1480.
46. (a) I.M. Spitz, and I. Agranat, Chem. Ind. (Lond), 1995;
89. (b) E.–E. Baulieu, The Abortion Pill: RU-486, A
Woman’s Choice, Simon & Shuster, New York, 1991. (c)
L. Lauder, RU-486: The Pill That Could End the Abortion
Wars Against Your Family and Why Women Don’t Have It,
Addison Wesley, Reading, MA, 1991.
47. Planned Parenthood Today, Spring 1996; 3 (published by
Planned Parenthood Federation of America, New York).
48. (a) S. Silver Wilmington Delaware News Journal 1997;
July 3:A14. (b) M. Balter, Science, 2000; 290:39.
49. (a) P.W. Collins, Kirk–Othmer Encyclopedia of Chemical
Technology 4th ed., 1996; 20:302. (b) V. Ullrich, and R.
Brugger, Angew. Chem. Int. Ed. Engl., 1994; 33:1911. (c)
Y. Sugimoto, A. Yamasaki, E. Segi, K.T. Tsuboi, Y. Aze,
T. Nishimura, H. Oida, N. Yoshida, T. Tanaka, M. Kat-
suyama, K.–Y. Hasumoto, T. Murata, M. Hirata, F.
Ushikubi, M. Negishi, A. Ichikawa, and S. Narumiya, Sci-
ence, 1997; 277:681.
50. (a) Letter, Planned Parenthood Federation of America,
New York, Oct. 1997. (b) K. Armstrong, Wilmington,
Delaware News Journal 1994; Oct. 17:A8. (c) D. Brown,
Wilmington, Delaware News Journal 1994; Oct. 19:A7.
51. W.R. Ewart and B. Winikoff, Science, 1998; 281:520.
52. (a) D.R. Gardner, R.J. Molyneux, L.F. James, K.E. Panter,
and B.L. Stegelmeier, J. Agric. Food Chem., 1994; 42:756.
(b) K.E. Panter, R.J. Molyneux, L.F. James, and B.L.
Stegelmeier, J. Agric. Food Chem., 1996; 44:3257. (c)
M.S. Al–Mahmoud, S.P. Ford, R.E. Short, D.B. Farley, L.
Christenson, and J.P.N. Rosazza, J Agric. Food Chem.
1995; 43:2154.
53. Science 1997; 278:1233.
54. (a) Univ. of Cal. Berkeley Wellness Lett., 1998; 15(1):4.
(b) R.S. Stephens, S. Kalman, C. Lammel, J. Fan, R.
Marathe, L. Aravina, W. Mitchell, L. Olinger, R.L.
Tatusov, Q. Zhao, E.V. Koonin, and R.W. Davis, Science,
1998; 282:754. (c) T. Hatch, Science, 1998; 282:638. (d)
T. Nordenberg, F.D.A. Consumer, 1999; 33(4):24.
55. B. Dixon, Biotechnology, 1994; 12:1314.
56. J.K. Sherwood, L. Zeitlin, K.J. Whaley, R.A. Cone, and M.
Saltzman, Nat. Biotechnol., 1996; 14:468.
57. G. Mathew, R.P. Singh, R. Lakshminarayanan, and S.
Thomas, J. Appl. Polym. Sci., 1996; 61:2035.
58. C.M. Roland, Rubber World, 1993; 208(3):15.
59. R. & D. (Cahners), 1997; 39(10):61.
60. Consumer Rep 1999; 64(6):46.
61. Popline, May/June 1992; 21:1 (Population Institute, Wash-
ington, DC).
62. M. Balter, Science, 1998; 282:1790.
63. J. Alper, Science, 1999; 284:1754.
64. A.M. Rouhi, Chem. Eng. News 1999; June 28:24.
65. Univ. Calif Berkeley Wellness Lett., 1995; 12(2):8.
66. (a) K.M. Reese, Chem. Eng. News, 1995; Apr 24:82. (b)
M. Wood, Agric. Res., 1999; 47(5):18.
67. N.R. Legge and R.C. Mowbray, Rubber World, 1994;
211(1):43.
Chapter 16
68. Chem. Ind. (Lond.), 1997; 157.
69. Popline Mar/Apr 1996; 18:4, (Population Institute, DC).
70. L. Gopinath, Chem. Br., 1997; 33(9):32.
71. Popline, May/June 1999; 21:3 (Population Institute, Wash-
ington, DC).
72. Wilmington, Delaware News Journal Oct. 7, 1997.
73. Chem. Eng. News. 1994; Sept. 5:35.
74. P. Aldhous, New Sci 1995; Mar 4:16.
75. (a) T. Black, Popline Jan/Feb 1996; 18:3 (Population Insti-
tute, Washington, DC). (b) Popline Mar/Apr 1999; 21:1
(Population Institute, Washington, DC). (e) http://www.
quinacrine.com.
76. P.F. Harrison, A. Rosenfield, Contraceptive Research and
Development—Looking to the Future, National Academy
Press, Washington, DC, 1996; 119.
77. R.A. Hatcher, ed. Contraceptive Technology, 17th ed. Ar-
dent Media, New York, 1998.
78. (a) V.D. Vacquier, Science 1998; 281:1995. (b) S. Tanaka,
T. Kunath, A.–K. Hadiantonakis, A. Nagy, J. Rossant, Sci-
ence 1998; 282:2072. (c) E. Strauss, Science 1999;
283:169. (d) Y. Chen, M.J. Cann, T.N. Litrin, V.
Iowigenko, M.L. Sinclair, L.R. Levin and J. Buck, Sci-
ence, 2000; 289:625. (e) M. Miyado, G. Yamada, S. Ya-
mada, H. Hasuwa, Y. Nakamura, F. Ryu, K. Suzuki, K.
Kosai, K. Inoue, A. Ogura, M. Okabe and E. Mekada, Sci-
ence 2000; 287:321.
79. P. Aldhous. Science 1994; 266:1484.
80. (a) S. Wilkinson, Chem Eng News 1997; June 30:9. (b)
D.J. Burks, R. Carballada, H.D.M. Moore, P.M. Saling,
Science 1995; 269:83. (c) R.J. Aitkin, Science 1995;
269:39. (d) L.H. Bookbinder, A. Cheng, J.D. Bleil Science
1995; 269:86.
81. (a) W.J. deKoning, G.A. Walsh, A.S. Wrynn, and D.R.
Headon, Biotechnology 1994; 12:988. (b) V. Garcia–Cam-
payo, A. Sato, B. Hirsch, T. Sugahara, M. Muyan, A.J.W.
Hsueh, I. Boime, Nat Biotechnol 1997; 15:663. (c) B.
Kutscher, M. Bernd, T. Beckers, E.E. Polymeropoulus, J.
Engel, Angew Chem Int Ed Engl 1997; 36:2149.
82. C. Djerassi, Science 1996; 272:1858.
83. (a) R.F. Service Science 1994; 266:1480, 1489. (b) S. Bor-
man, Chem Eng News 1996; June 3:6. (c) R.F. Service,
Science 1996; 272:1258.
84. Science 1995; 268:791.
85. K. Michelman. Letter to NARAL members, Oct 1997.
86. G. Feldt, Letter to Planned Parenthood Federation of
America members, Aug 1997.
87. J. Cohen, Science 1997; 277:760.
88. (a) K. Mahadevan, M. Sumangala, Social Development,
Cultural Change and Fertility Decline: A Study of Fertil-
ity Change in Kerala. Sage, New Delhi, 1989. (b) B. McK-
ibben, Hope, Human and Wild: True Stories of Living
Lightly on the Earth, Hungry Mind, St Paul, MN, 1995. (c)
R. Jeffrey, Politics, Women and Well-Being: How Kerala
Became a “Model.” Macmillan Academic & Professional,
London, 1992. (d) B.A. Prakash, Kerala’s Economy, Per-
formance, Problems, Prospects, Sage, New Delhi, 1994.
(e) R.W. Franke, B.H. Chasin, Radical Reform as Devel-
Population and the Environment
opment in an Indian State, 2nd ed, Institute for Food De-
velopment Policy, Oakland, CA, 1994.
89. K.M. Leisinger, K. Schmitt, All Our People—Population
Policy with a Human Face, Island Press, Washington, DC,
1994.
90. (a) Union of Concerned Scientists, Poverty, Development
and the Environment, Cambridge, MA, May 1994. (b)
Popline July/Aug 1999; 21:2 (Population Institute, Wash-
ington, DC).
91. Popline 1997; July/Aug:3 (Population Institute, Washing-
ton, DC).
92. (a) Letter from W Fornos (Population Institute, Washing-
ton, DC), Sept 1999. (b) World Watch 1999; 12(1):39. (c)
U.N. Development Programme, Human Development Re-
port 1998, Oxford University Press, New York, 1998,
30–37.
93. G. Feeney, Science 1994; 266:1518.
94. Popline 1995; May/June: 2 (Population Institute, Wash-
ington, DC).
95. M. Renner. In: L. Starke, ed., State of the World 1995,
W.W. Norton, New York, 1995; 150.
96. G.H. Brundtland, Environment, 1994; 36(10):16.
97. N. Myers, People Planet, 1993; 2(2):37.
98. K. Krane, Amicus J., 1994; 16(3):45.
99. (a) Anon., Chem. Ind. (London), 2000:484. (b) Anon.
Popline, July-August 2000; 22:2.
100. Institute for Development Training, 212 E. Rosemary
Street, Chapel Hill, North Carolina 27514, Feb. 2000.
495
RECOMMENDED READING
1. D.W. Hahn, J.L. McGuire and G. Bialy, Kirk–Othmer Ency-
clopedia of Chemical Technology, 4th ed., 1993; 7:219 [con-
traceptives].
2. L.R. Brown. In: L. Starke, ed. State of the World 1995, W.W.
Norton, New York, 3. [“Nature’s Limits”].
3. P. Harrison, The Third Revolution: Population and a Sustain-
able World, I.B. Tauris, New York, 1992; 255. [differences in
consumption between the rich and the poor].
4. J. Bongaarts. Science, 1998; 282:419. [declining fertility and
future population trends in the world].
5. L.R. Brown and B. Halweil, World Watch, 1999; 12(5):20.
[effects of increasing populations on the environment].
EXERCISES
1. What family-planning services are available in your
community for both rich and poor?
2. Check with your local department of health to see
what the rates of teenage pregnancy; infant mortal-
ity; AIDS, and other sexually transmitted diseases;
rape; and births are in the area where you live or go
to school.
3. Was sex education in your home and school thor-
ough and realistic?
4. Do you know some people with large families? If it
is possible to do so tactfully, see what their attitudes
are toward zero population growth.
17
Environmental Economics
I. INTRODUCTION
The previous chapters have covered many ways of reduc-
ing pollution by prevention. This is often cheaper than
putting something on the end of the pipe or the top of the
smokestack. For example, substitution of an aqueous
cleaning process for one using trichloroethylene means
that no solvent has to be purchased, or recycled, or dis-
posed of. No solvent emissions result from the new pro-
cess, and none can be spilled and seep into the ground wa-
ter. The used water can be treated on site or at the local
wastewater treatment plant. Processes that will help soci-
ety attain a sustainable future have also been discussed.
According to Ed Wasserman, president of the American
Chemical Society for 1999, “Green chemistry is effective,
profitable and it is the right thing to do for our health and
that of our planet.”1 The problem is that companies and
ordinary citizens have been slow to adopt these new pro-
cesses.2 This chapter will explore what role money plays
in this and what other social and political factors may be
involved.
Under conventional economics, market forces can de-
stroy or profoundly affect the life support system on which
we depend. This destruction is now evident in worldwide
problems, such as stratospheric ozone depletion, and global
warming. On a smaller scale, a commercially important
species can be driven to near extinction by ordinary market
forces.3 The striped bass fishery on the East Coast of the
United States provided fish for the restaurant trade. As the
supply of fish was reduced by overfishing, the restaurants
charged more and customers were willing to pay the price.
Finally, when the population was seriously depleted, the
federal government initiated a moratorium on fishing for
the species. After a few years without harvesting, the pop-
ulation began to recover.
497
A new hybrid discipline of environmental economics
(also called ecological economics) tries to include the value
of natural support systems in a consideration of profit and
loss. Ecologists and economists are coming to know each
other. The International Society for Ecological Economics
publishes the journal Ecological Economics. A number of
reviews of the subject are available.4
II. NATURE’S SERVICES
Nature provides a number of important services5 free of
charge. These are seldom included in economic calcula-
tions. Robert Costanza and co-workers have estimated their
total value at $33 trillion/yr.6 (The authors emphasize that
these figures are preliminary and will require further re-
finement in the future.) For comparison, the world’s gross
national product per year is about 18 trillion dollars. The
gross annual national product of the United States is 6.9
trillion dollars. The 17 services were estimated for 16 dif-
ferent biomes, including forest, grassland, wetlands, ocean,
and so on. They included
Gas regulation: composition of the atmosphere, ozone
layer, etc.
Climate regulation: temperature, precipitation, etc.
Disturbance regulation: resilience to storms, droughts,
etc.
Water regulation: the hydrologic cycle
Water supply: storage and retention of water, aquifers
Erosion and sedimentation control
Soil formation
Nutrient cycling: nitrogen, phosphorus, etc.
Waste treatment: recovery of nutrients
Pollination
Biological pest control
498
Refugia: nursery grounds, overwintering grounds, etc.
Food production: fish, game, etc.
Raw materials: lumber, fuel, fodder, etc.
Genetic resources: medicines, genes for resistance to
pests
Recreation: ecotourism, sport fishing, etc.
Cultural: aesthetic, artistic, educational, or scientific
value
The largest value, 17 trillion dollars, is assigned to nutrient
cycling.
Because ecosystem services are often ignored or under-
valued, the social costs of a project may exceed the bene-
fits. As an example, clear-cutting a forest will produce in-
come for the landowner, the timber company, and the
workers. It will also decrease the value of nearby homes.
The sediment that washes off in the process may make the
streams unsuitable for spawning fish, fill up reservoirs, and
kill the coral reef in the ocean where the stream enters it.
When it rains, more water will run off and less will soak
into the ground. Floods will occur more often. Another re-
sult may be that the stream now dries up in the summer so
that the adjacent town has no water to drink or to use in ir-
rigating crops. If these services could be replicated at all,
the cost would be high. The water might be brought in by
pipes from another watershed. The fish might be imported
from another part of the globe. The electricity from the lost
hydropower might be supplied by a new coal-burning
plant.
Such natural services may be interrupted in other ways.
If the chemical or sewage plant upstream puts something
toxic into the stream that the water treatment plant of the
city downstream cannot remove by standard treatments, a
new water supply or a new treatment method will have to
be found at increased cost. In earlier years before the toxi-
city of the polychlorinated biphenyls was fully appreciated,
General Electric released enough of them into the Hudson
River north of Albany, New York that the whole Hudson
River from Hudson Falls to New York City is now a Su-
perfund site.7 Fishermen are advised not to eat the fish that
they catch. It is not always easy to calculate the cost of a
fishery lost to toxic heavy metal ions or acids draining out
of a mine site.8 One settlement, involving a salmon fishery
in a river in Idaho, was for 60 million dollars. The Exxon
Valdez oil spill in Alaska cost Exxon 3 billion dollars. The
persons whose wells become contaminated by leachate
from the nearby landfill will face the costs of bringing wa-
ter from a distance. This was a cost that was not included
when the landfill was built. The U. S. National Research
Council has recommended that the U. S. Department of
Commerce resume development of a method to better mea-
sure environmental costs.9
Chapter 17
The economic value of biodiversity has also been calcu-
lated by others.10 Pimentel and co-workers11 estimate the
value of biodiversity at $3 trillion/y. Their list of services
includes the following:
Soil formation
Biological nitrogen fixation
Crop and livestock genetics
Biological pest control
Plant pollination
Pharmaceuticals
They point out that biodiversity is necessary for the sus-
tainability of agricultural, forest, and natural ecosystems on
which humans depend. Roughly 99% of pests are con-
trolled by natural enemies and by plant resistance. Loss of
key pollinators may mean loss of a crop. Honeybees can
pollinate some crops, but not all of them. There are already
species for which no pollinators are left.12 Current extinc-
tion rates are 1000–10,000 times the natural rate. The con-
cern is that keystone species (i.e., species without which
the ecosystem cannot function) may be lost. These are
more likely to be soil microbes or insects than pandas or
tigers, despite the popular appeal of the latter.
Just the extent of human alteration of the natural cycles
is causing problems. Soil microbes and lightning fix about
90–140 million tons of nitrogen each year. Humans add
140 million more tons as fertilizer made by the chemical in-
dustry to increase crop yields.13 This has accelerated the
loss of biodiversity. Nitrogen is a key element in control-
ling species composition, diversity, and dynamics in both
terrestrial and aquatic systems. Many of the original native
plants function best at low levels of nitrogen. Many soils
are now so saturated with nitrate that vital nutrients, such as
calcium and potassium ions, are being lost to groundwater
and streams. Algal blooms and toxic Pfiesteria outbreaks
are more common. This has contributed to long-term de-
clines in coastal fisheries. There is now, as a result of fer-
tilizer runoff from midwestern farms, a large area in the
Gulf of Mexico with too little dissolved oxygen to support
the fishery. Some of the nitrogen is released to the air as
N2O, a greenhouse gas that helps to deplete the ozone layer.
(Other ways of handling nitrogen for agricultural purposes
were given in Chap. 11.)
According to one source14 “degradation of our natural
environment continues accelerating in scope and impact”
under the pretext of the economic necessity “to balance
budgets” and to provide opportunities for “development.”
Another author feels that growth and trade are increasingly
incompatible with environmental protection.15 Others even
question the advantages of continuing economic growth in
developed nations that are already overconsuming.16 Yet,
Environmental Economics 499

almost every issue of Chemical Engineering News men-
tions the desire to grow, to produce, and to sell more.
The chemical industry relies on natural capital,17 which
must be used in a sustainable way. This means that the pre-
sent generation should fill its needs in a way that does not
jeopardize the prospects of future generations.18 It means
that natural ecosystems must not be exploited to a point at
which they lack the resilience to recover.19 Traditional eco-
nomics views natural capital as endless or easy to substitute
for, so that one can use it and move on to more of it some-
where else. All that is needed to exploit it is labor and
money. During most of human’s existence on earth, this
may have seemed true. Today, the limits of the earth20 are
apparent, and the frontier philosophy must be replaced by
an ethic of looking out for what we have, so that it will last
indefinitely. Extractive industries, such as timbering and
mining, must produce products no faster than the trees can
grow back or renewable substitutes can be found for the
minerals.21 Each person living in Germany, Japan, The
Netherlands, and the United States consumes 45–85 metric
tons of natural resources each year.22 In the subsidized
mining of coal in Germany, 29 metric tons of earth, per per-
son in Germany is moved each year. Most of this is waste.
In the United States, 15 metric tons of topsoil per person
per year is lost as part of agricultural production. These hid-
den costs do not appear in the usual economic statistics.
With the continuing decline in the concentration of the de-
sired metal or mineral in the rock, the time may come when
the landfills of today are mined for metals. The figure for
gross national product often contains money from products
harvested unsustainably.
III. ENVIRONMENTAL ACCOUNTING
A. The Ecological Footprint
Table 17.1 Typical Values of Land or Water Needed to
Support a Person
Country Land or water needed (ha/person)
United States 5.1
Canada 4.3
Netherlands 3.3
India 0.4
World 1.8
that is unsustainable, pollution and waste in the supplier na-
tion that does not show up on the balance sheet of the con-
suming nation.
Calculation of the ecological footprints of the cities
around the Baltic Sea showed that the area required for the
assimilation of their waste nitrogen, phosphorus, and car-
bon dioxide would be 390–975 times the land area of the
cities.24 The amount of forest land needed to assimilate the
carbon dioxide from all the world’s cities would be three
times that available on earth.
B. Life Cycle Analyses
Environmental life cycle analyses follow a product from
cradle to grave.25 They may not be easy to do and they may
be expensive. They have to take into account the environ-
mental effect at each stage; the raw materials and the way
they were obtained; the manufacturing process; any trans-
portation involved; the influence of use and how the object
will be disposed of at the end of its useful life. When no
hard data from detailed studies is available, simplifying as-
sumptions may have to be made. It is not surprising that
different persons evaluating the same product can come to
different conclusions. The first thing to do in looking at an

Each year, 6 million ha of land in the world undergo deser-

tification, 17 million ha are deforested, and soil erosion ex- Table 17.2 Typical Land and Water
ceeds soil formation by 26 billion tons. The ecological Deficits by Country
footprint is an accounting tool devised by William Rees to
measure the productive land area needed to supply the re- Country Deficits
source consumption and waste assimilation of a given hu- Japan 1.76
man population.23 Twenty percent of the world’s popula- Korea 1.81
tion, largely in industrialized nations, consumes 80% of its Austria 2.15
resources. Some typical values of the productive land or Belgium 2.8
water needed to support a person at a given material stan- United Kingdom 2.65
dard indefinitely are shown in Table 17.1. Denmark 2.38
Many developed nations do not have enough productive France 2.22
land or water to support the current material consumption. German 2.66
Typical deficits are given in Table 17.2. Netherlands 2.85
Switzerland 2.56
Materials to make up the deficits are supplied by other
United States 2.29
nations. Thus, there may be natural resource exploitation
500
analysis is to see if the group that funded it might have a
vested interest in the outcome.26 The second thing to do is
to see what assumptions have been made.
Several studies have compared the environmental ef-
fects of disposable diapers with cloth diapers.27 A 1988
analysis by the cloth diaper industry favored cloth as hav-
ing a smaller environmental effect. A 1990 study made for
Procter & Gamble, makers of disposable diapers, favored
disposable diapers. A 1990 study by the American Paper
Institute found the two kinds to be equivalent. A 1991 study
by the cloth diaper industry found cloth to be superior.
A disposable diaper is often made with a nonwoven
polypropylene fiber face sheet and transfer layer next to the
skin, backed by a layer of cellulose and a superabsorbent
polymer, with a polyethylene cover on the outside. Over
the years they have become thinner. The polyethylene and
polypropylene are unlikely to have been made from renew-
able raw materials, although it is conceivable that they
might be in the distant future. The superabsorbent may or
may not have been made at least partially from starch.
Thus, one must assess the possibility of oil spills in drilling
for and recovering the oil. What wastes were associated
with this? Was any forest destroyed in the process? What
pollution or wastes came out of the oil refinery? What type
of forest was cut to produce the cellulose? Was old-growth
forest cut? Did the logging result in sediment damaging a
fishery or in other loss of biodiversity? What pollution and
wastes were involved in making the superabsorbent? The
acrylonitrile that may have been grafted to starch to pro-
duce the superabsorbent is a carcinogen. What was the en-
ergy needed to make the diaper and to transport it to the
user? The energy probably came from fossil fuel, rather
than from a renewable source. What was the fuel efficiency
of the equipment used in the various steps of acquiring the
raw materials, making the diaper, and transporting it. After
use, the diaper probably was buried in a landfill where even
the cellulose part may not decompose. (Landfill cores have
often been dated by the dates of the newspapers found in
them.)
The cotton diaper also involves the use of energy that
probably comes from fossil fuels. Again, what was the fuel
efficiency of the equipment used in the various steps in the
life cycle? The cotton may have been raised with subsi-
dized irrigation water and with pesticides and fertilizers,
some of which may have seeped into the groundwater or
the nearest stream. Were the workers in the cotton mill pro-
tected from dust? Because the diaper can be used many
times, the main environmental effect will involve making
the detergent, the washing machine, and heating the water.
What wastes and pollution may have accompanied the
making of the detergent? Is the energy to heat the water
from a fossil fuel or a renewable source? What is the energy
Chapter 17
efficiency of the water heater? How much hot water is
used? Swedish clothes washers may take only a small frac-
tion of the water used in an automatic clothes washer in the
United States. How hot is the water? Is the detergent used
in warm water instead of hot water? Is the diaper dried on
a line in the sun or in a drier powered by gas or electricity?
Are two worn diapers sewn together to obtain more life
from them? When the child no longer needs the diapers,
will they given to a friend who will use them until they
wear out? At the end of their useful life, will the diapers be
used as wiping clothes, in rag content paper, or just sent to
the landfill? How do you depreciate the washing machine
that is used to wash other clothes as well?
One of the studies of cloth diapers assumed a life of 92
uses (a study funded by the disposable industry), whereas
the other assumed 167 uses (a study funded by the cloth di-
aper industry). A study funded by the disposable diaper in-
dustry assumed an energy cost for transporting the cotton
to China where the diapers were made. One would have to
check to see what fraction of cloth diapers are made this
way. Disposable diaper makers have pushed composting as
a method of disposal. Most cities do not compost this type
of waste. The polyolefins would not degrade well in this
process, even though the lack of stabilizers in the
polypropylene might allow it to become powder.
This comparison of diapers shows how many assump-
tions and judgment calls have to be made in typical life cy-
cle analyses. To perform a comprehensive analysis would
require collecting a large amount of data that might be ex-
pensive to obtain. It also points out the possible misuse of
data. A diaper that involved no use of nonrenewable mate-
rials would be preferred. It is also likely that if a study does
not reach the conclusion desired by the sponsor, the data
may never be released. In some other comparisons, longer-
lived alternatives are neglected. Attempts to compare the
environmental effects of throwaway paper and plastic cups
do not include the china mug. The mug will take more en-
ergy to make, but it can last for decades. During its life it
could be washed using soap or detergents and energy from
renewable sources. It would have the least effect on the en-
vironment. Comparisons of paper and plastic grocery bags
overlook the possibility of bringing your own basket or
string bag. For shopping in a supermarket several string
bags would do the job, with the least effect on the
environment.
Life cycle assessment is a technique that is still evolv-
ing. The U.S. Environmental Protection Agency (EPA) is
studying the technique and trying to standardize it enough
to allow meaningful ecolabels to be put on consumer
items.28 Among the effects being considered are ozone de-
pletion, global warming, smog formation, human toxicity,
noise, energy use, and nonrenewable resource depletion.
Environmental Economics
Trade-offs may sometimes have to be made (e.g., choosing
the lesser influence of toxic chemical use and global warm-
ing). The process endeavors to quantify “energy and raw
material requirements, atmospheric emissions, waterborne
emissions, solid wastes, and other releases for the entire life
cycle of a product, package, process, material, or activity.”
A factor that should be included is whether or not the prod-
uct has been designed for easy disassembly for recycle at
the end of its useful life. Many other countries have gov-
ernment-sanctioned ecolabeling programs, including the
European Community, Canada, France, Germany, Austria,
The Netherlands, Singapore, New Zealand, and Japan. Al-
though these may differ in detail, the goal is to promote
products that have reduced environmental effects during
their entire life cycles. They should also help consumers
make informed choices in their purchases. This will help
avoid goods that unintentionally promote a dysfunctional
economy.
C. Cost–Benefit Analyses
Cost–benefit analyses29 can also involve uncertainties and
trade-offs. Some of the biggest problems involve health
and safety. What value should be assigned to a human life?
Will this value be the same for a person in a developing na-
tion as it is in a developed one? How can the cost of sick-
ness be measured? One can add up the costs of doctor’s vis-
its, medicines, and income lost from missing work. What
dollar value can be put on time lost from school or the mis-
ery of just feeling lousy? Lead in the environment can
lower the IQ of children. What dollar value should be as-
signed to this? What lost value is assigned to a dirty lake?
Does one add up the cost of buying fish instead of pulling
them out of the lake, the cost of driving elsewhere to fish or
swim, and the cost of cleaning up the water for drinking?
Cost–benefit analyses have been popular with some
members of the U. S. Congress, who hope that new regula-
tions can really be justified economically.30 However, that
the benefits are significantly larger than the cost31 has not
eliminated the grumbling when the cost of the change is
high. Such was true with the lowering the ozone standard
from 0.12 to 0.08 ppm and reducing the size of the particu-
late matter to be regulated.32 The new regulations were es-
timated to prevent 20,000 premature deaths per year and
250,000 sick days. The cost would be $6.5–8.5 billion/y
versus benefits of 120 billion dollars. The new particulate
standards could require redesign of diesel engines in trucks
and buses, as well as putting new catalytic converters on
wood stoves. Changes in coal-burning power plants may
also be required.
The U. S. Environmental Protection Agency has been
credited with doing a good job with cost–benefit analy-
501
ses.33 The analyses are said to be explicit and transparent,
with all the assumptions stated. The cost of each analysis
for lead in gasoline, asbestos, ozone depletion, and such,
ran from 731,000 to 1,035,000 dollars. When the underly-
ing science is good, the analyses can be helpful. If it is
weak, there may be no point in running the analysis. Ac-
cording to EPA calculations, huge benefits have resulted
from the Clean Air Act over the period of 1970–1990.34
The cost was 523 billion dollars and the benefits 6–50 tril-
lion dollars. Curbing acid rain in the United States under
the Clean Air Amendments of 1990 produced 12 dollars in
benefits, of reduced illnesses and deaths and better visibil-
ity, for every 1 dollar in compliance costs.35
D. Green Accounting
Pollution and waste represent inefficiencies of produc-
tion,36 which might be eliminated through pollution pre-
vention.37 For example, if the United States were as en-
ergy-efficient as Sweden or Japan, it could save $200
billion/y. The chemical industry in the United States
spends over 4 billion dollars each year on pollution control,
an amount equal to 2.7% of sales.38 An additional 2.1% of
sales is spent on related capital expenditures.
Antiquated accounting systems are one hindrance to the
identification of opportunities for pollution prevention.
The costs of waste may be hidden in overhead, research and
development, marketing, product registration, and other
unrelated accounts.39 The waste and all costs associated
with it should be assigned to the process and product that
produces it. This may turn out to be as much as 20% of the
total production cost of the product. Amoco’s Yorktown,
Virginia, oil refinery thought its environmental costs were
3% of operations, until it checked carefully and found them
to be 22%.40 duPont found a case where the environmental
costs were 19% of the manufacturing costs. When the true
cost is properly assigned, management may have a greater
incentive to restudy the whole process in the search for a
better one. The pollution prevention alternative may offer
opportunities for increased productivity and reduced cost.
It can be cheaper than any end-of-the-pipe treatment. It
may eliminate the need for waste disposal, especially dis-
posal of hazardous waste, scrubbers on exit air, need to re-
port toxic releases, future liabilities, and contingencies,
such as fines or need to remediate spills. For example, if the
solvent is replaced by water, there will be no need for an air
scrubber. No solvent will need to be purchased. If no toxic
reagents are used, then none will be left in exit air or water.
If a use can be found for the waste, it will generate revenue,
rather than require a disposal fee. If no waste is sent to a
landfill, then none will leach out in the event of a failure of
the liner and there will be no long-term liability. In addi-
502
tion, a clean process may help the corporate image, which
may help sales of other products as well. Capital requests
for pollution prevention projects will fare better in compe-
tition with other capital requests if all these factors are
taken into account. Plants with green-accounting systems
have roughly three times as many pollution prevention pro-
jects as those with no cost-accounting system. The projects
yielded an average savings of 3.49 dollars for every dollar
spent.41 A study by the Business Roundtable (a group of
top executives of large corporations) concluded that pollu-
tion prevention efforts can be successful when they are in-
corporated into existing business procedures, rather than
being treated in separate plans, and when specific ap-
proaches are not mandated.42
Many plants have associated costs that are not borne by
the plant, but which are externalized to others. These are
also referred to as societal costs. These are not included in
the usual accounting system. Businesses may not be legally
accountable for them. Consider, for example, the power
plant that burns high-sulfur coal. Some such plants have
scrubbers that take out most of the sulfur dioxide from the
stack gas. Other plants were in existence when the Clean
Air Act went into effect and are grandfathered so that no
scrubber is required.43 In one place along the Ohio River,
an old plant puts out six times more sulfur dioxide per unit
of electricity generated as a nearby newer plant. The air re-
ceiving the sulfur dioxide drifts eastward to New York and
New England where it decreases forest and crop yields and
can kill some forests. Tall stacks put on some plants in the
midwest reduce the concentration of sulfur dioxide at
ground level locally, but increase long-range transport. The
sulfur dioxide is converted to sulfuric acid in the air. This
causes corrosion of objects made of metal, limestone, mar-
ble, and sandstone. These include automobiles, which have
to have an acid-resistant finish, power lines, buildings, stat-
ues, and others. In former years, sulfur oxides from metal
smelters often killed all vegetation within miles of the
smelter, as at INCO’s smelter in Sudbury, Ontario. (After
resisting clean-up for many years, INCO found that imple-
menting a redesigned smelting process not only reduced
emissions, but also reduced costs, so that it made a return
on its investment.44 It now markets the technology.) High
concentrations of sulfur oxides in smog in London and in
Donora, Pennsylvania, killed many persons in the 1950s.
There is an incentive to keep the grandfathered plants run-
ning as long as possible because they are cheaper. The cost
of adding scrubbers would raise the price of electricity to
customers in Ohio, but not to the point that their electricity
would be more expensive than that in New England.
In former years, the city of Philadelphia used what it
thought was the most cost-effective system of handling the
city’s wastewater. This involved only primary treatment
Chapter 17
(i.e., simple filtration to remove solids). The solids were
transported to the ocean by barge for dumping. The filtrate
was dumped directly into the Delaware River. The result
was a section of the Delaware River that contained too lit-
tle dissolved oxygen for fish to survive. Migratory fish,
such as shad, could not go up the river past this block.
Swimming was no longer possible at the former beaches
near New Castle, Delaware. In one summer, these waste
solids, together with wastewater from New Jersey rivers
caused an area of 2000 square miles of ocean to have too
little dissolved oxygen to support life. The ocean could no
longer be considered an infinite sink for wastes. This sys-
tem was probably cheaper for residents of Philadelphia, but
it was not for its neighbors downstream. It took years of lit-
igation and a suit by the states of Delaware and New Jersey
plus several environmental organizations to persuade
Philadelphia to put in plants for secondary treatment of the
wastewater. The federal government put up the bulk of the
money to build the new plants.
Individuals can also export some of their costs to their
neighbors. Agricultural runoff of soil, pesticides, and fer-
tilizer can lead to algal blooms, Pfiesteria outbreaks, loss
of fish, and loss of biodiversity. Leaky septic tanks can
contaminate groundwater and surface water. Soil erosion
from construction sites can plug culverts, fill up reservoirs
and harbors, and such. Because the downstream costs from
construction fall on government, more and more regula-
tions are being put into place to try to keep the costs on the
construction site. Development of a site often leads to
greater runoff of water in storms, which can lead to stream-
bank erosion. Regulations are now being aimed at water re-
tention basins that will keep the excess water and costs on
site. Individuals also operate cars with tailpipe emissions
that can cause smog and contribute to acid rain. The costs
of these are borne by the general public, especially those
with respiratory problems. Although efforts are being made
by government to regulate this, many states still violate the
standards for groundlevel ozone several days each summer.
The cost of picking up litter along roads falls on the tax-
payers or on the people who live along the road.
One problem in some of these examples is the diffuse
nature of the effects. The public may not be able to associ-
ate the problems with the real source, which may be far
away. Because the effects can be diffuse, it may be hard to
obtain enough persons together to mount a strong lobby for
relief. Some lobbies are not as effective as others. Based on
what has happened in the Pacific Northwest of the United
States, the timbering lobby appears to be much stronger
than that of the salmon fishermen. Campaign contributions
may be part of the problem. A logging company may be
able to afford larger contributions than individual fisher-
men. Some environmentalists feel very strongly about this
Environmental Economics
problem. Donella Meadows of Dartmouth has said, “The
first priority is campaign reforms. We’re lost until we get
democracy back.”45 Accounting methods that reflect the
true cost of these various actions to society are needed.
IV. CORPORATIONS
A. Additional Reasons That Pollution
Prevention May Not Be Adopted
Incomplete accounting is not the only reason for the slow-
ness of businesses to adopt pollution prevention.46 Several
pollution prevention opportunities were identified at a Dow
plant in Texas that manufactures isocyanates.47 The sav-
ings would have been $1 million/yr with payback periods
ranging from 15 months to 5 years. The new processes
would have eliminated 500,000 lb of waste each year and
allowed the hazardous waste incinerator to be closed. The
changes were not made because the business center thought
that more money could be made by other investments. A 2-
year study of Dow’s Midland, Michigan, plant by a team of
community activists and company project engineers (orga-
nized by the Natural Resources Defense Council) revealed
opportunities for a 37% reduction in waste and a 43% re-
duction in emissions at a capital expense of 3.1 million dol-
lars and a potential savings of $5.4 million/yr.48 It will be
interesting to see how many of these changes are adopted.
A Dow plant in Louisiana has annual waste reduction con-
tests that have produced a stream of improvements over
several years.49 Problems that often prevent implementa-
tion at other places were said to be absent at this plant.
These include (a) fear of losing control over funds, (b) giv-
ing prevention a low priority, and (c) a belief that the new
process would not work.
Paul Tebo of duPont has outlined his company’s inten-
tion to reduce emissions and waste with the goal of zero
emissions.50 He says that proactive companies are finding
that what is good for the environment is good for business
and can lead to a competitive advantage. An example he
gives is the company’s nylon plant at Chattanooga, Ten-
nessee, which now converts 99.8% of the raw materials to
saleable products. As a result, the site’s wastewater plant
will be shut down and the remaining wastewater sent to the
city’s treatment plant, which will save $250,000/yr. This
has been done by finding uses for by-products that were
discarded. (By-products of duPont’s manufacture of nylon
were discussed in Chap. 1.) A second example is a new her-
bicide plant in Indonesia that will produce only one or two
bags of ash each week from its solid and liquid waste. New
plants are more likely to incorporate pollution prevention
than old ones that are fully depreciated, especially if the
products of the old one are considered to be mature and are
503
not growing in sales. Ecoparks, where one company’s
waste is another’s raw material, may become more com-
mon.51 An example is the one at Kalundborg, Denmark52
(described in Chap. 14).
OSi Specialties, a subsidiary of Witco, was nudged into
action by the U. S. Environmental Protection Agency.53
The problem was loss of methyl and ethyl chloride in the
wastewater from a process of making ethers from polyethy-
lene oxide and polypropylene oxide. A complete study of
all of the waste streams at the plant resulted in a solution
that cost 600,000 dollars and saved 800,000 dollars. This
was done by adding a unit that converted the excess methyl
chloride from the process to methanol, which could be
sold. An attorney for the company says, “But if it hadn’t
made economic sense, we wouldn’t have done it.” If
dimethyl carbonate could be used for the end-capping,
there would be no waste salts produced and almost no
wastewater.
A study done by INFORM found that the “obstacles to
pollution prevention were not regulatory, technological or
even economic, but primarily institutional.”54 Most com-
panies assumed that their processes were efficient. Some
pollution control departments had little knowledge of the
processes that produced the wastes that they handled. An-
other study found that environmental managers often lack
the whole-hearted support of the company’s business man-
agers, so that it is hard for them to get things done.55
The U. S. Department of Energy has found that seven in-
dustrial sectors; chemicals, aluminum, steel, metal casting,
glass, petroleum refining, and forest products, consume
80% of the energy used in manufacturing in the United
States and are responsible for 80% of all waste and pollu-
tion from manufacturing.56 Research and development av-
erages about 2.8% of sales for all manufacturing in the
country. Aside from the chemical industry, the six other seg-
ments spend about one-third of this. These industries have
relatively mature markets and technologies. Their scale re-
quires large capital expenditures for change, and payback
periods may be long. They are characterized by conserva-
tive investment strategies and a reluctance to innovate. This
has led to high pollution, high energy use,140 and little in-
centive to improve. According to the Department of Energy
(DOE), the chemical industry spends more on research and
development than the average manufacturer. However,
most of this is said to be on product development, rather than
on basic research or research to improve processes. The
DOE is putting up some federal money to help companies
in these industries to innovate in areas where the companies
are unlikely to innovate on their own, but for which the pay-
offs may be large for the whole country.
Individuals may not act in the best interests of the com-
pany if personal incentives are not right.57 Managers are of-
504
ten averse to risk. Because pollution prevention projects
can involve both effort and risk, the managers must be
compensated accordingly, or some system must be devised
to shift the risk from the managers to the firm. The whole-
hearted support of top management for pollution preven-
tion also helps. Without it, such projects may become low-
priority ones. One study of 12 large manufacturers showed
that small projects were subjected to higher hurdles than
large ones by middle management.58 It suggests grouping
several small projects into one large one to achieve the at-
tention of top management.
A company that has downsized to the point where many
employees have too much work to do may have little time
to do more than service existing product lines. Manage-
ment may have little incentive to invest money or research
in product lines that are not growing and that it considers to
be mature. Too much emphasis on the bottom line next
quarter may lead to a demand for unrealistically short pay-
back times for pollution prevention projects. There have
been cases where a plant manager looked good on the bal-
ance sheet by spending very little money for maintenance.
That this approach may end up costing more in the long run
than planned preventive maintenance may not become ap-
parent until the plant manager has transferred to another lo-
cation or has retired. For example, a small leak in the roof
will do little damage if fixed promptly. If it is allowed to re-
main until it becomes large, the repairs may include not
only new roofing but also the beams that support the roof,
the ceiling and floors in the room below, and any equip-
ment in the rooms that would be damaged by water. Man-
agement may also be wary of a pollution prevention project
that it feels falls under someone else’s patent. It may feel
that any royalty charged might be enough to negate any
cost savings that might result from the project. It may also
look at end-of-the-pipe treatments as simpler and easier
than reexamining their whole process to find ways to im-
prove it. There may also be the fear that the new process
will not pay for itself in savings, with the result that com-
petitors who do not clean up will have an advantage in the
marketplace. If management feels that a better environ-
mental technology is just around the corner, it may fear
locking into a process that might be obsolete in a few years.
A drop-in replacement that requires no new equipment is
more likely to be adopted than one that requires major pur-
chases of new equipment. If more equipment has to be
added to space that is not in the present plant, then the cost
of expanding the building must be considered. Some pro-
cess changes can involve major changes to equipment un-
familiar to the current personnel. For example, discharge of
heavy metal ions in the wastewater from an electroplating
plant can be avoided by vacuum metallization, chemical va-
por deposition, and other such. The equipment will be quite
Chapter 17
different and expensive, and the plant personnel may dis-
trust it because they are not familiar with it. Older engineers
may recall problems with newer methods in former years,
before the techniques were improved to current levels. The
use of ultrasound and microwaves in organic reactions may
fall into this category. Aqueous degreasing to replace chlo-
rinated solvents may be distrusted for fear of rusting.
Prompt removal of water with a jet of air, or inclusion of cor-
rosion inhibitors, can prevent the formation of rust. A syn-
thetic organic chemist may not know how to run a fermen-
tation, even though doing so might eliminate toxic reagents
and hazardous wastes as well as organic solvents.59
A municipality may not improve its wastewater treat-
ment plant because its officials were elected on the promise
of no new taxes. The electorate may not vote for any new
bonds to be issued either.
B. Other Aspects of Corporate Finance
The high cost of accidents involving toxic chemicals was
mentioned in Chap. 1. In a fire or explosion, there is the
cost of rebuilding the plant, the possible loss of business to
competitors during the period when your plant cannot sup-
ply, hospital and rehabilitation bills for the injured, gov-
ernment fines for safety violations, awards by juries for
damage to the community, and loss of a good company im-
age that may have helped to sell your products. This should
provide a powerful incentive for substituting greener pro-
cesses that use less toxic chemicals. In addition to the rea-
sons for accidents in Chap. 1, there may also be the feeling
that “It can’t happen here.” “We’ve been doing it this way
for years and have never had a problem.”
Corporations are often said to place their interests over
those of the community, the state, and the environment.60 It
is to their financial advantage to externalize as many costs
as possible, rather than internalize them. After the logging
company removes the timber in some countries, replanting
may be left to the government. This is in addition to the
downstream loss of fisheries mentioned earlier. A genera-
tion or two ago in the United States, beer and soft drinks
were sold in refillable bottles with deposits on them. Since
then, the bottlers have turned to single-use throwaway con-
tainers. The washing lines have been dismantled and their
crews laid off or shifted to other jobs. The consuming pub-
lic pays more now for the packaging and for its disposal.
The local government usually provides the landfill or in-
cinerator to deal with the packaging after it is used (see also
Chap. 14). Firms may tend to overexploit costless inputs
such as air and water, in what Hardin called the “tragedy of
the commons.”
Firms are in business to make money. This sometimes
results in abuses, such as unsustainable use of raw materi-
Environmental Economics
als, or contamination of air and water. In a typical situation,
the more the firm sells, the more money it makes. This
hardly encourages conservation. Ways are needed by
which a corporation can make more money by selling less
material. A few ways have been found to do this. duPont
has a contract with a major auto company to paint the new
cars. This provides an incentive to minimize the amount of
paint used. If it just provided the paint in the usual way, the
way to maximize the profit would be to sell more paint per
car. Businesses may use less material, but make just as
much money, by leasing, servicing, and taking back equip-
ment, as they could by selling it and letting the customer
take care of its disposal at the end of its useful life. If done
properly, the leasing and servicing system could build up
customer loyalty. Some of the parts in obsolete equipment
might be reused in updated new models. Interface, a carpet
company in Georgia, leases its flooring products to cus-
tomers who return it when it is worn out so that Interface
can recycle it into new flooring materials.61 Xerox saves
hundreds of millions of dollars each year with its programs
to reuse and recycle photocopiers.62 Old machines are up-
dated by replacing modules in the same housing.
Little work is done on drugs for major tropical diseases
because the pharmaceutical industry fears that the persons
who contract the illnesses will be too poor to purchase the
drugs.63 However, some drug companies have sold drugs
of questionable benefit in developing countries.
Many firms that make money by supplying fossil fuels
are reluctant to diversify into energy-supply companies.
They could also make money by selling and servicing
equipment and techniques of energy conservation, or by
selling energy from renewable sources. However, the tech-
niques for obtaining energy from renewable sources may
be unfamiliar to them. Electric power plants could sell
more energy if they used their waste heat for district heat-
ing and cooling, instead of putting it into a river (see also
Chap. 15). Some public utilities commissions in New Eng-
land have worked out systems for rewarding utilities for
selling energy conservation to their customers so that less
electricity needs to be generated.
A firm in the business of selling agricultural chemicals
might diversify into integrated pest management. This
would mean fewer employees in chemical plants, but many
more employees as ecologists, entomologists, soil scien-
tists, and such, to monitor insect populations, crop damage,
fertilizer needs, or other. Such firms could sell consulting
services. They might also obtain patents on insect traps,
pheromones, or insect repellents, on which they could ob-
tain royalties on the use by others. (Agricultural chemicals
are covered in Chap 11.)
These examples show a switch from pure manufacturing
to broader companies that provide a variety of services as
505
well as products. Unfortunately, large firms are less inno-
vative than small ones and are often reluctant to make the
kinds of changes suggested here. The changes would in-
volve the retraining of workers no longer needed in pro-
duction, but the new company structure would require
more total employees. As far as consumer products are
concerned, it often takes more labor to repair one than to
produce a new one by mass production methods.64 This
overlooks the cost of disposal.
V. ENVIRONMENTAL ECONOMICS OF
INDIVIDUALS
A. Making Choices
Individuals try to minimize their expenses, but they do not
always buy or do what is cheapest, at least not what is the
cheapest per unit of performance, or cheapest over the
long-term. They sometimes justify this in terms of in-
creased “convenience.” Some of this is a matter of what
dollar value they place on their time that is not spent at
work earning money. The leaf blower is much more ex-
pensive and uses more materials and fossil fuel than a rake
that is used by hand. Yet, they seem to be increasing in pop-
ularity. The use of single-use throwaway beverage contain-
ers, which are more expensive than refillable ones on a per
trip basis, was mentioned earlier. A similar situation exists
in fast-food restaurants. Throwaway dishes and eating
utensils cost more per use than washable, reusable ones.
They are popular with the restaurant management because
no equipment, labor, or space are required for washing
them. Consumers often buy less efficient items, such as
fuel-inefficient vans, justifying their purchases by “conve-
nience” and “I can afford it.” They may also buy for style
and fashion, rather than longer life and better wear.
There are often hidden costs not seen by the consumer
when he or she makes his or her choice. Stores in America
create the illusion of abundance and perpetuate the myth of
plenty. Few consumers see the natural resource depletion
and unsustainable nature of this. The environmental abuse
that created the object may be well out of sight, thousands
of miles away. Buying a teak bench or tropical hardwood
paneling may involve destruction of tropical forests by un-
sustainable harvesting. Wild flowers are popular with
home gardeners. Buying them may contribute to the deci-
mation of natural populations if the plants are collected
from the wild. The situation is not helped by nurserymen
who collect from the wild, then grow the plants in their
nurseries for a year and label them as “nursery grown.”
Ecolabels will help consumers make informed choices only
if the labels are honest. This may require certification by an
unimpeachable agency, possibly by government.
506
The purchase of food may involve similar hidden
costs. The food may have been raised on land that for-
merly was a diverse forest or prairie. It may have in-
volved heavy use of pesticides and soil loss. Because the
average food item consumed in the United States has been
shipped over a thousand miles, the energy cost in dis-
tributing it is high. Buying local produce would reduce
this energy cost. Without informative labels, how can the
shopper tell the difference? People may inadvertently
contribute to the loss of local farm products by buying a
new house on what may have been some of the best farm-
land in the state. This will eventually raise food prices be-
cause the yields from marginal land will be lower or food
will have to come from farther away. People who buy wa-
terfront lots, complete with a boat slip at the back of the
house, may not think about the productive wetland that
was replaced, but may be disappointed at the decline in
the fish populations that they came to catch. The abuser
may be far away from the problem that he or she helped
to create. A farmer in Lancaster County, Pennsylvania
who uses a lot of fertilizer in the hope of maximizing his
crop yields may not realize that he is contributing to the
decline of life in the Chesapeake Bay downstream (i.e.,
unless he goes to the Bay to fish or sail in his off time).
The motorists who change their own oil and pour it down
the storm drain or sewer may not realize that they are de-
grading the river below where they like to fish on week-
ends. Nor are they thinking of the extra cost to the next
town below to purify the river water for drinking. The
amount that goes into the waterways of the United States
this way each year is about 430 million L, compared with
the 45 million L spilled by the Exxon Valdez in Alaska a
few years ago.65 These are examples of “social traps” in
which short-term goals and narrow interests lead to out-
comes that no one wants.66
There is a tendency of Americans to buy by the lowest
initial price, rather than the lowest price per unit of time.
Passive solar heating and cooling raises the initial cost of a
home, but lowers the cost of home ownership over a period
of years. Outdoor paint that will last for 3 years will prob-
ably be cheaper than paint that will last for 5 years. How-
ever, it is not cheaper per unit of performance when the
time, labor, and money involved in repainting every 3 years
is considered.
People may think that a problem they can not see is not
real, as in the case of global warming or depletion of the
ozone layer. They may also give no thought to what hap-
pens to their trash after they put it at the curb to be collected
or what happens after they flush the toilet. Landfills, incin-
erators, and wastewater treatment plants have all been big
problems for some communities. Some Superfund sites are
former landfills.
Chapter 17
Green consumers can take effective action against busi-
nesses that are not environmentally responsible in some
cases. If the business markets a product directly to con-
sumers, a consumer boycott of its products may be effec-
tive in persuading the company to change. Such was the
case when a European company promoted its baby formula
over breast feeding in Africa. If the offending firm markets
only to other firms that then make the consumer products,
the boycotts may be less effective. Putting a correcting res-
olution on the ballot for the next annual meeting of the
shareholders can call attention to the problem. Such reso-
lutions seldom win, but sometimes the company would
prefer to settle the complaint than have a major confronta-
tion at the annual meeting.
B. Ecotourism
Ecotourism is becoming big business.67 If done properly, it
can be an important way of preserving biodiversity and
bringing income to the area. However, there are limits. The
actions of the tourists must not be so much that they de-
grade the area, or tourists will stop coming. In Sri Lanka,
the coast was degraded by the lack of proper disposal
means for garbage and wastewater.68 Trekking in the Hi-
malayan Mountains has resulted in deforestation and litter
accumulation along trails.69 Tourism in Bali has resulted in
the fragmentation and degradation of coastal ecosystems of
coral reefs, seagrass, and mangroves.70 The message in all
of these cases is that proper service facilities must be pro-
vided for the tourists who come. The amount and extent of
resource use should be planned in advance by the commu-
nity and the businesses there. Recreational diving in east-
ern Australia involved breakage of 0.6–1.9 corals per 30-
min dive.71 The bulk of the damage was done by a small
number of inexperienced divers. Predive briefing helped
reduce the problem. Because the most damaging activity of
all was the anchoring of the boats that brought the divers,
putting in established moorings should help.
A big fish on the reef in front of underwater photogra-
phers will bring in much more money than the same fish on
the end of a fishing line. Many more people will see it on
the reef. The small coral reef fish are more valuable for
tourism than they would be in someone’s home aquarium
thousands of miles away. There can be other abuses as
well. A man whose family is hungry may poach the wild
game to eat or to sell to outsiders who will pay a lot for it.
A person who uses poisons or blast fishing in Indonesian
coral reefs destroys the reef for short-term personal gain at
the expense of long-term gain for the whole community.72
These types of problems can be minimized by systems that
channel at least some of the money from tourism to the peo-
ple who live there, instead of it all going to the trekking
Environmental Economics
company or the hotel. It is estimated that if the coral reefs
in Milne Bay, Papua New Guinea are left in pristine condi-
tion, they will be worth more in tourism revenues than rev-
enues from all other local industries combined.73 Bird
watching at Cape May, New Jersey, on the Atlantic migra-
tion flyway, is big business, bringing 31 million dollars to
the area each year.74 Each year 18.1 billion dollars is spent
on viewing wildlife in the United States.
Networks of no-take marine refuges have been proposed
as a way to protect biodiversity as well as tourism. If suit-
ably placed, these refuges would provide fish and fish eggs
and larvae, for other areas where fish have been overhar-
vested.75 The concept is good, but it is proving difficult to
put into practice. The key impediment is the long tradition
of free access to fish in the ocean commons in spite of the
evidence of damage due to overfishing. This is another ex-
ample of the “tragedy of the commons.” This has caused
the proposed no-take part of the Florida Keys National Ma-
rine Sanctuary to shrink from 10% of the total to less than
0.5%, an amount that may be too small to be effective.
VI. GOVERNMENT ACTIONS AFFECTING
ENVIRONMENTAL ECONOMICS
A. The Role of Government
The interplay of the market place can allow results to hap-
pen that are not in the long-term interest of society. For
example, it can drive a species to extinction. It can so de-
grade the “commons” of air and water that they can no
longer provide the free natural services that they once did.
Government can provide a series of incentives to encour-
age individuals and businesses to manage these resources
in a sustainable way.76 It can set up accreditation systems
to certify that a product has been produced in an environ-
mentally sound fashion (e.g., a green label indicating that
the tropical wood has been harvested in a sustainable
manner).77 Germany has used a government-regulated
“Blue Angel” logo on environmentally sound products,
such as mercury-free thermometers, for the past 20
years.78 Voluntary labeling of wood grown on a sustain-
able basis and crops produced by organic-farming meth-
ods is being tried.79 It is endorsed by environmental orga-
nizations. Such systems need independent verification of
compliance. Such certification may offer some competi-
tive advantage.
Most of the current regulations in the United States are
based on considerations of health and safety.80 In some
cases, it has been necessary to use a precautionary princi-
ple and act when the problem is definite, but before the fi-
nal scientific evidence is in, as in the Montreal Protocol for
substances that deplete the ozone layer.81 As problems of
507
ozone depletion, global warming, and loss of biodiversity
have reached global dimensions, international treaties
among many nations have become necessary to address the
problems.82 International institutions, such as the World
Bank, as well as governments, are working harder to pre-
vent further damage to our life support system, the earth.83
The State Environment Protection Inspectorate of
Poland is trying to improve Poland’s poor environmental
record by a “name and shame” policy of publishing a list of
the country’s polluters each year.84 Since 1990, the list has
dropped from 80 to 69.
Governments can establish laws to restrict abuses. If
something is terribly bad, it can be banned completely, as
happened in the United States in the banning of seed treat-
ments involving organomercury compounds. Mercury is
involved in enough fish advisories that setting a limit of
zero on wastewater may be desirable. This would cause a
shift of any remaining chlorine plants using mercury elec-
trodes to the well-proved method using Nafion-containing
cells. (Taiwan had seven plants still using the mercury pro-
cess in 1999. One of them made the news in 1999 when
Formosa Plastics shipped 3000 metric tons of mercury-
containing waste to Cambodia, where it was rejected.85 At-
tempts to have it treated in California failed, so that the
waste went back to Taiwan, where the people do not want
it either. Taiwan has been slow to adopt adequate controls
on environmental pollution.) Putting a zero limit on toxic
heavy metal ions in wastewater might allow sewage sludge
to change from something that is hard to get rid of to a prof-
itable soil amendment. A law proposed in Vermont would
require labeling of consumer products containing mercury,
to help in recycling them.86 Manufacturers of fluorescent
lamps oppose this law.
Undesirable practices can be taxed and the money used
to subsidize desirable ones. An example would be a tax on
an automobile that had poor fuel efficiency, with the sub-
sidy going to one with high fuel efficiency. Government
can collect and distribute information on pollution preven-
tion. It can require that information for consumers be in-
cluded on product labels (e.g., nutritional labels on food
packages). It can use seed money to support research,
sometimes jointly with businesses. Preserves can be set up
to protect biodiversity.87
Some of these systems have worked well, but many
have been criticized by those affected and others. Some of
the regulatory systems are cumbersome and need stream-
lining. It is not always easy to tell whether the law, or its in-
terpretation, is flawed, or those being regulated are just
grumbling because they would prefer not to be regulated.
The system is still evolving, sometimes in different ways in
different countries. We still lack effective systems for deal-
ing with some of the problems of the “commons.” All in-
508
volved need to work toward more effective systems that
will lead all of us into a sustainable future.
B. Regulations
Regulations88 have proved to be quite valuable in curbing
some of the worst pollution of air and water from point
sources. They have been less effective in handling pollu-
tion from nonpoint sources. Just the threat of regulation
can cause companies to study ways to reduce their pollu-
tion. Many efficient, profitable ways of reducing pollution
tend to surface after regulations go into effect.89 Regula-
tions can reduce a firm’s resistance to change. They can
also provide a level playing field where a company that
cleans up at some cost is not penalized in the marketplace
by losing market share to one that has not. Penalties for
noncompliance must be high enough to hurt the com-
pany’s bottom line, so that they are not just considered as
part of doing business. (Some businesses that would pre-
fer to avoid the costs of complying with regulations quote
the costs without mentioning the benefits and call for
“regulatory reform.”90)
Industry in the United States has argued for greater flex-
ibility in correcting the problems than is allowed in some of
the command-and-control laws. It says that this will allow
it to seek the least-cost solutions to problems. This has
started to happen. The case of OSi Specialties cited earlier
involved the U. S. EPA and the company in a plant-wide
approach. The U. S. Occupational Safety and Health Ad-
ministration (OSHA) has now invited each of the compa-
nies with the worst safety records to implement an im-
proved safety and health program, with the guarantee that
there will be significant worker involvement.91 A pilot
study of this method in Maine lowered the injury rate 30%.
However, on a national scale, the program has been halted
by a court ruling in a suit brought by the National Associa-
tion of Manufacturers.92 The court ruled that OSHA did not
follow the proper procedures in implementing the plan.
“Cap and trade” systems allow the polluter more flexi-
bility in finding the least-cost way to comply.93 The gov-
ernment puts a cap on the amount of a pollutant that can be
emitted (at a lower level than found at the time). For sulfur
dioxide emissions in the United States this was set at half
of the former level. A company that cleaned up to more
than this level was given credits to sell to one that could not
meet the 50%. This led to the desired reduction of emis-
sions 30% ahead of schedule at one-tenth the cost of some
industry predictions.94 This involved use of low-sulfur coal
instead of adding scrubbers. This should offer an additional
incentive to improve methods for reducing the sulfur levels
in mined coal. This method has been proposed for tackling
the problem of global warming. It is being used in northern
Chapter 17
New Jersey to limit the amount of mercury entering the Pa-
saic River.95 A proposal has been made to lump all the pol-
lutants from one site in a single trading credit, instead of
having separate credits for each one.96 These and other
market-based environmental tools have been endorsed
widely.97 For the protection of biodiversity, these include
disincentives such as access fees, user fees, and noncom-
pliance fees, as well as cost sharing of reserves, individual
fishing quotas, trading rights, and such.
Deposit–refund systems work, as shown in nine states in
the United States and in many other countries. They are ef-
fective in eliminating improper disposal, as well as reclaim-
ing a sorted, relatively uncontaminated stream for recycling.
About 60% of the aluminum beverage cans used in the
United States are recycled. However, in Vermont the de-
posit returns over 90% of them. Copying the Vermont ex-
ample with a federal law covering the entire country would
eliminate an enormous amount of waste and natural re-
source depletion. Deposit–refund systems for lead–acid bat-
teries and lubricating oils have been suggested. Although
most lead–acid batteries are recycled, some still find their
way into landfills and incinerators from which they can
cause pollution. The problem of improper disposal of lubri-
cating oil was discussed earlier. Recovering it would allow
it to be cleaned up for reuse. Extended product responsibil-
ity is being used in Germany. More takeback requirements
for manufacturers could lead to greater repair and reuse, as
well as to less waste and more recycle.98 A similar system
might be used on standardized nestable or collapsible ship-
ping containers for a variety of goods. Governments can
help industry standardize sizes so that items can be reused
by just changing the label to that of the new company. Beer
and wine bottles are handled this way in Germany.
Right-to-know laws have been successful in reducing
pollution in the United States. They were enacted in the af-
termath of the disaster at Bhopal, India. The Toxic Release
Inventory, begun in 1986, requires polluters to quantify
their emissions annually99 (see also Chap. 1). Frequently,
top-level managers had been unaware of the extent of emis-
sions. The law has been a powerful incentive to reduce
emissions. Companies are afraid of losing business if their
corporate image is tarnished. Being listed in the local paper
as the biggest polluter in the area or being put on a “dirty
dozen” list is undesirable from their standpoint. Ten firms
with “grandfathered” plants in Texas have announced that
they will voluntarily reduce emissions by 10,000 tons
annually.100
Massachusetts and New Jersey have gone a step further
and require information about the movement of toxic
chemicals within plants.101 The laws also require the plants
to produce proposals to reduce the amounts of hazardous
chemicals used. In the period of 1990–1995, by-products
Environmental Economics
were reduced 30% and toxic chemical use 20%. Cost sav-
ings were reported by 67% of the nearly 600 companies in-
volved. The benefits to the state are estimated to be 91 mil-
lion dollars, which exceeded costs by 77 million dollars,
even when excluding human health and ecological bene-
fits, which are hard to monetize. Only 12% of the compa-
nies wanted the program eliminated. This included the
Massachusetts Chemical Technology Alliance, a trade as-
sociation, in conjunction with the American Chemistry
Council (formerly the Chemical Manufacturers Associa-
tion).102 The New Jersey law directs the companies to pre-
pare a pollution prevention plan. This costs an average of
26,000 dollars. For every dollar spent on the process, facil-
ities predict a net savings of 5–8 dollars with a payback pe-
riod of 1–2 years.
California has a law, enacted in 1986, Proposition 65,
that requires manufacturers to list on the label of their
products any significant amounts of compounds in them
that might cause cancer or have reproductive toxicity.103
This has prompted companies to reformulate their products
to remove such materials.
C. Jobs and Regulations
Hueting104 mentions three myths in the environmental de-
bate that must be reversed for progress to be made: (a) The
environment conflicts with employment. (b) Production
must grow to create financing. (c) It is too expensive for so-
ciety to save the environment. There is no evidence that en-
vironmental regulations in the United States have harmed
the economy.105 States with stronger environmental pro-
grams outperformed states with weaker programs. In the pe-
riod 1965–1990, levels of carbon monoxide, sulfur dioxide,
and lead were reduced in southern California. During this
same period, employment grew 50% above the national av-
erage, wages were above the national average, and so was
the local economy. Nations with the most stringent envi-
ronmental regulations show the best economic perfor-
mance. Plants with poor environmental records are no more
profitable than cleaner plants in the same industry.106 There
is no evidence that superior environmental performance
puts a company at a disadvantage in the marketplace. Only
about 0.1% of layoffs are due to environmental regulation.
The relocation of jobs offshore is mainly due to lower labor
costs, not to environmental regulation. A shift to a sustain-
able economy is expected to create more jobs in energy ef-
ficiency, recycling, and public transportation, than will be
lost in the oil and coal industries, car manufacturing, and
waste disposal. Other jobs will appear in wind energy, pho-
tovoltaic cells, bike path construction, and so on.141
Environmental spending creates jobs in part because the
business is labor-intensive and often uses capital goods that
509
are produced domestically.107 There are more than 100,000
environmental technology firms in the United States.108
They employ 1.3 million people and make 180 billion dol-
lars each year. Their exports are $16 billion/yr and provide
a 9.3 billion dollar trade surplus. World markets for the en-
vironmental technology industries were 295 billion dollars
in 1992.109 The industry is driven by regulation. Its growth
may slow, at least in the industrialized nations, as major
sources of pollution are brought under control. The next
step will to devise new processes that meet the environ-
mental and productivity needs of industry.110 As an exam-
ple, this includes jobs created when a new business is set up
to make products from recycled materials.111 It can also in-
clude a new machine that does a better job (e.g., the May-
tag front-loading washing machine which handles larger
loads in a gentler fashion than the usual top-loading ma-
chine, while saving water and electricity).112 Further work
is needed to reduce the price, which at present, is twice that
of the top loader.
As for the myth that production must grow to create fi-
nancing, most growth comes from the most environmen-
tally damaging activities. This includes natural resource
depletion, carbon dioxide emissions, and other such. The
myth that it is too expensive to save the environment is
wrong. Using a hand rake instead of the leaf blower saves
materials, energy, and dollars. Use of a bicycle instead of
driving alone in your car shows similar savings. Raising
two children instead of six is much cheaper and impinges
much less on the environment. The combination of eco-
nomic growth and conservation will be possible in a sus-
tainable economy that does not deplete natural capital and
in which clean technologies are no more expensive than
current ones when all the costs are considered.
D. Subsidies
The market is distorted by the many subsidies provided by
governments. Subsidies more than $500 billion/yr are
given to environmentally destructive activities.113 Many of
these subsidies shore up declining extractive industries.
Coal mining in Germany is an example. In the United
States, these include below-cost timber sales in the national
forests, cheap mining claims, irrigation water provided by
dams built at public expense, grazing fees for public lands
that are too low for sustainable use, price supports for crops
raised in monoculture, highway construction, and policing
costs not assigned to the automobile.114 Those who use nat-
ural capital should be expected to pay the full cost of it,115
as suggested in a report on the United States written by the
Organization for Economic Cooperation and Develop-
ment. If they did, they might use less of it, and recycled ma-
terials could compete better in the markets. The National
510
Recycling Coalition in the United States urges the elimina-
tion of subsidies so that recycled materials can compete
better with virgin materials.116 The price of petroleum in
the United States is artificially low, which encourages its
wasteful use (as described in Chap. 15). Worldwide subsi-
dies to fossil fuels amount to $58–300 billion/yr.117 The
subsidy to fossil fuels in the United States is $25
billion/yr.118 The subsidy for water for western agriculture
in the United States is $4.4 billion/yr.119 The U. S. Depart-
ment of Agriculture also pays farmers to keep 28 million
acres of marginal crop land out of production in a Conser-
vation Reserve Program.120 Subsidy-driven overcapitaliza-
tion of the world’s fishing fleets has resulted in drastic de-
clines in many fish populations.121
Some authors feel that governments, whether Brazil or
the United States, tend to perpetuate the status quo, com-
plete with favors to special interests.122 Subsidies allow in-
efficiencies to remain in the system. Subsidies, if used,
should be taken off virgin materials and put on to recycled
ones. They should be removed from energy-inefficient
forms of transportation and given to the energy-efficient
ones. They might also be used to jump-start new technolo-
gies for a sustainable future. This was done in California
for wind energy. Subsidies in the form of tax relief or joint
research projects with industry might be used to put pollu-
tion prevention processes into plants.
E. Taxes
Green taxes may be the least costly way to a sustainable fu-
ture.123 Taxes on waste, pollution, and on environmentally
damaging products, such as pesticides, fertilizers, motor
vehicles, fuels, as well as unsustainable natural resource
depletion, have been proposed.124 Such ecotaxes are being
tested in Europe.125 Many of these taxes are revenue-neu-
tral, the money being put back into the same industries in
the form of reductions in other taxes. The amount put back
can favor those industries with the most efficient processes
producing the least pollution. These include taxes on car-
bon dioxide, sulfur dioxide, and nitrogen oxide emissions;
lead in gasoline, fertilizer, and batteries in Sweden; toxic
waste and water pollution in Germany; water pollution and
household waste in The Netherlands; a carbon dioxide tax
in Norway; and water pollution in France. Other taxes are
also becoming more common. Denmark taxes cars and
trucks by weight, which is often related to fuel efficiency.
It also has a tax on disposable beverage containers, plates,
cups, and cutlery. There are also taxes on paper and plastic
carrier bags, pesticides in containers smaller than 1 kg,
nickel–cadmium batteries, and incandescent light bulbs.
Belgium has a tax on disposable razors that are not recy-
cled, as well as one on disposable beer bottles. In Australia,
Chapter 17
products made entirely from recycled paper are exempt
from the sales tax. All of these are designed to shift taxes
away from labor and capital and on to energy and the en-
vironment. The taxes appear to be working.126 Taxes on
heavy-metal emissions in The Netherlands have cut emis-
sions of mercury 97%. Iowa has reduced fertilizer use by a
tax on it.127 Similar taxes have been proposed to cut fertil-
izer use in Europe.128 Denmark’s waste tax reduced waste
26% from 1987 to 1997, with recycling going up at the
same time.129 England is studying the use of ecotaxes to
improve the environment.130 There is a movement to make
the ecotaxes uniform over the European Union.131 China
has proposed taxes on wastewater, noise, solid waste, and
low-level radioactive waste.132
Regulatory taxation of fossil fuels is favored as a means
of combating global warming.133 However, the European
chemical industry is against energy taxes for fear that these
could hinder its ability to compete with companies in other
countries (e.g., the United States) where energy is
cheaper.134 A study by the World Resources Institute fa-
vors taxing pollution, congestion, and waste, instead of
payrolls, incomes, and profits.135 The taxes would include
tolls on congested urban highways, taxes on the carbon
content of fuels, and fees for collecting household waste. A
study by the Worldwatch Institute proposes a shift of taxes
from wages and profits to pollution and resource deple-
tion.136 The study predicts that this would create jobs and
boost living standards without damaging industrial com-
petitiveness and without increasing the overall tax burden.
The American Chemistry Council is opposed to the idea.
Some of the common objections to pollution taxes, which
may not be valid, are that they are a license to pollute, may
be accepted as a cost of doing business and that they may
be harshest on smaller firms.137
Green taxes must not be dodged by firms bringing in
products made in other countries that do not have them.
Tariffs on imported products could neutralize this.138 Tar-
iffs could be removed on clean technology and products
produced with them. One proposal is to handle this by giv-
ing a country most sustainable nation status, in the same
way that the United States gives most favored nation status
to others for trading purposes. This could translate into low
or no tariffs for a country using sustainable harvesting of
resources.
Another change in government rules might eliminate a
practice of some firms that try to delay cleaning up by lit-
igation, feeling that legal fees are cheaper than cleaning
up.139 The proposal is to have the U. S. Securities and Ex-
change Commission require companies to report haz-
ardous waste sites as financial liabilities. This would
show up in the company’s bottom line until the site was
cleaned up.
Environmental Economics
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RECOMMENDED READING
1. D.M. Roodman. In: L. Starke, ed. State of the World 1996.
W.W. Norton, New York, 1996; 168 [taxing pollution and
waste].
2. S. Nathan. Chem Ind (Lond) 1995; 824 [green taxes in Eu-
rope].
3. Chem Eng News 1995; Mar 20:17 [slowness of industries to
adopt pollution prevention].
4. D. Pimentel, C. Wilson, C. McCullum, R. Huang, P. Dwen,
J. Flack, Q. Tran, T. Saltman, B. Cliff. Bioscience 1997;
47:747 [value of biodiversity].
5. C. Crossen. Tainted Truth: The Manipulation of Fact in
America. Simon & Schuster, New York, 1994; 140–143 [life-
cycle analyses of diapers].
6. R.U. Ayres. Environ Sci Technol 1998; 32:366A [“toward a
zero-emissions economy”].
EXERCISES
1. How would you revise the tax system to favor a
clean environment and a sustainable future?
2. What does your state or country subsidize?
3. Does your state or country offer any flexible, mar-
ket-based alternatives to the “command-and-con-
trol” system of reducing pollution?
4. Do a life cycle analysis of some commonly used
item (e.g., a paper napkin versus a linen napkin or a
natural versus an artificial Christmas tree).
5. What factors would have to be taken into account in
a cost–benefit analysis of a regulation to outlaw the
release of mercury into water?
6. List some individuals or groups or firms in your ar-
eas that externalize some of their costs at the ex-
pense of the public.
18
Greening
I. INTRODUCTION
Chapter 17 described some economic and institutional fac-
tors that slow down the adoption of pollution prevention.
This chapter continues this theme by considering the extent
to which individuals, governments, and businesses have
embraced the concepts of a clean environment and a sus-
tainable future.
Rachel Carson pointed out the dangers of the indiscrim-
inate use of pesticides in her book Silent Spring, published
in 1962.1 Gaylord Nelson, a former senator from Wiscon-
sin, originated Earth Day, the first one being held in 1970.2
These are two of the major events that gave rise to the en-
vironmental movement of today in the United States. The
United States Congress responded to this movement by en-
acting the Clean Air Act, the Clean Water Act, and the En-
dangered Species Act, as well as other laws. What has hap-
pened since then? One poll conducted in the United States
in 1994 found that 23% of the respondents considered
themselves to be active environmentalists, and 56% were
sympathetic to the environmental cause.3 More than half
felt that environmental laws had not gone far enough, with
only 16% feeling that the laws had gone too far. Environ-
mental groups were considered favorably by 74% of the
respondents.
Progress has been made in some areas since 1970. Emis-
sions of pollutants from point sources into air and water
have decreased. Toxic releases are decreasing. Some Su-
perfund sites have been cleaned up. Businesses would no
longer think of dumping a barrel of waste solvent on the
ground at the landfill site so that the barrel could be used
again for the same purpose. Control of pollutants from non-
point sources is still a problem. There is now more interna-
tional cooperation and discussion of global problems, such
as ozone depletion by chlorofluorocarbons and the effect of
517
population growth on the environment. Several nations
have achieved zero population growth rates. Population
growth rates are still high in some of the developing nations
least able to deal with them. A great many of the world’s
fisheries are overfished. Biodiversity continues to decline.
More consumer goods are marked with the postconsumer
recycled content. Many of these problems have been dealt
with in earlier chapters. By analyzing the greening that has
occurred during this period, it may be possible to find ways
to speed up the process of attacking the remaining prob-
lems.
II. INDIVIDUALS
Many persons who say that they are green may be so only
in limited ways, owing to problems that they do not associ-
ate themselves with or do not understand.4 Use the quiz be-
low to see how green you are.
1. What do you put on your lawn?
2. What do you take off your lawn and what do you
do with it?
3. What do you use to carry the groceries in after you
buy them?
4. What toxic chemicals do you have in your home
and garage?
5. Do you use any single-use, throwaway items?
6. How many cars of what type are there in your fam-
ily?
7. How long has it been since you rode on a train?
8. What do you do with the used oil taken from your
car?
9. How do you dry the washed clothes?
10. How often do you mend an object instead of dis-
carding it and buying a new one?
518
11. What do you do with clothes or toys that the chil-
dren have outgrown?
12. Do you have anything in your home or office that
was made using toxic chemicals?
13. Do you own anything made of teak or mahogany?
14. What do you recycle?
15. How many children do you have or intend to
have?
16. When did you last contact your congressman?
17. Does your home or office have active or passive
solar heating and cooling? Could these be added?
18. Does the wastewater from your toilet receive ter-
tiary treatment?
19. How many suits or dresses do you own?
20. How far do you live from work?
Readers will recognize what many of these questions
are getting at from the material given in earlier chapters.
Runoff from lawns, golf courses, and farms contaminates
many streams, decreasing the biodiversity in them. About
18% of municipal solid waste is yard waste. If you put
grass clippings or leaves in the trash can you are contribut-
ing to the landfill problem. Several of the questions are di-
rected at using less material and less energy. Groceries can
be carried in string bags, or in your own basket. There are
many times where you can substitute reusable items for
single-use ones. Mending something can substitute for
buying a new one. Passing things that you no longer need
on to friends can eliminate their need to buy something.
Living close to where you work may allow you to get there
by walking or cycling. Taking the train instead of your car
or an airplane can save energy. So can drying the wash on
an outdoor line. There is nothing wrong with changing your
own oil in your car. The problem is that about half of it ends
up going down storm drains to contaminate streams.
You may have a surprising number of chemicals con-
sidered to be hazardous in your home. These include pesti-
cides, lye for cleaning drains, hydrocarbon solvents for
cleaning, paints, varnishes, and others. Check the list of
chemicals that household hazardous waste drives try to col-
lect. Figuring out what you own that was made with toxic
chemicals will be more of a job. You can probably figure
out what formaldehyde was used to make, but beyond that
it may be difficult. Do not forget that the gasoline in your
car was probably made using an alkylation step catalyzed
by hydrogen fluoride or sulfuric acid. The leather in your
shoes was probably tanned with a chromium salt. For the
person with a chemical background, a search of industrial
encyclopedias and books on industrial chemistry may help
you decide what toxic chemicals were used. It is also true
that some toxic chemicals are so useful that it will be a long
time before they are displaced. Acrylonitrile and ethylene
Chapter 18
oxide fall in this class. If the company that made the item
that you are using has a consumer services telephone num-
ber, you can ask them what hazardous chemicals were used
in its manufacture. They may or may not tell you.
Some problems are not recognized because they are out
of sight. Most people probably do not know whether or not
the local wastewater treatment plant has tertiary treatment.
It may not have, especially if residents defeated the last ref-
erendum for a bond issue to build such a facility. They may
not know that their septic tank is leaking, if the leak is di-
rectly into a stream or lake. They may not know what land-
fill or incinerator their trash goes to. They may not realize
that the teak and mahogany that they value probably come
from overharvested tropical forests. Destruction of natural
forest may also be taking place on their own property if
they buy a new home on land that was forest or if they re-
move all native shrubs and wild flowers from a wooded lot
so that they can plant grass. There is also a feeling that the
environmental problem is caused by someone else. People
may blame the ozone alerts in the summer on emissions
from local manufacturing plants, rather than from too many
people driving in too many cars, as they drive alone in their
cars. They may be forced to drive because they lobbied
against pedestrianways between developments, against
sidewalks along roads, and against retail businesses any-
where near their homes. It may be easy to recognize a well-
publicized problem and miss others. A home near the au-
thor’s has a bumper sticker on the car to support recycling.
It also has an underground piping system for spray irriga-
tion of the lawn. This keeps the lawn green during the hot,
dry summer when the grass would normally go dormant. At
the same time, the county has tried to decide whether to de-
stroy a productive wetland or a wooded valley for a reser-
voir to meet the needs for more water for the future.
Consumer choices can make a difference.5 If no one
took the plastic grocery bags at the store, they would no
longer be offered. Americans like shiny cars with glamour
finishes. If they could settle for a finish more like that on a
truck or lawn mower, solvent would no longer be needed to
apply the finish coat. In Delaware, this could mean the
elimination of over 1 million lb of solvent emissions per
year from the two automobile assembly plants in the state.
Energy efficiency could be increased if consumers heeded
the energy efficiency ratings on new cars and appliances.
Energy would be saved and tailpipe emissions reduced if
they bought small cars instead of vans, sport utility wag-
ons, and pickup trucks. Wood is a renewable form of en-
ergy, but if a person buys and uses a wood stove without a
catalytic combustion aid in the stack, the stove will be a
source of air pollution. It is difficult for consumers to test
different brands on their own. However, they may be able
to obtain the information needed to make an intelligent de-
Greening
cision from a consumer-testing group such as Consumer
Reports. It takes effort to be really green. It may mean more
time in the library and more time shopping around for a
reusable item instead of the throwaway version that is more
common in the stores. It also takes extra effort to read the
green logo that the manufacturer has put on a product to de-
termine that it is really meaningful and that important
points, which might be negative, have not been left out.
Green consumerism is said to be making a difference and is
pushing manufacturers into offering products that are
friendlier to the environment.6
There are times when consumers work against the better
environmental choice. This usually happens when the fear
of the unknown and a lack of seeing the overall picture pro-
duces a “not in my backyard” response. Piggyback rail ser-
vice, where the truck trailers are hauled long distances on
trains, then unloaded for local delivery, saves energy.
However, when a proposal was made to add such service to
an existing railyard in Elsmere, Delaware, all the local res-
idents could think of was more trucks on local roads. “Stop
Chessie” bumper stickers appeared and the facility was
never put in. A good use for treated wastewater is to spray
it on to land to increase crop yields. Although research over
two or more decades has shown the method to be sound,
some neighbors of the project near Odessa, Delaware, were
still afraid. The facility is now in operation. Land applica-
tion of sewage sludge as a soil amendment is also hard for
some people to accept. Although fluoridation of water is
the best method known for preventing dental caries, some
groups still prevent its use in some cities. Although every-
one produces the trash, no one wants the landfill near where
one lives.
A single individual or family may feel helpless in trying
to green the country or the world. One person can make a
difference. Rachel Carson did it with her book, Silent
Spring (published in 1962) that described the overuse of
persistent pesticides. When the book was published it re-
ceived both favorable7 and unfavorable8 reviews. She was
criticized by companies that made insecticides and by gov-
ernment agencies favoring their use. Her writing was said
to present a “one-sided picture” and to contain “highly dra-
maticized presentations.” A 1987 review presented a more
moderate appraisal.9 A 1997 biography points out that she
checked her facts meticulously and that in many points, she
was right.10 A 1997 letter still says that there are inaccura-
cies in the book.11 Another writer feels that she was basi-
cally correct in what she wrote.12 Theo Colburn has called
attention to the environmental threats posed by hormone-
disrupting chemicals.13 She and her co-workers have called
attention to what may prove to an important problem, cer-
tainly one that justifies further research. Her book has also
been condemned by “book should be ignored” and “science
519
is missing.” This is almost a replay of the 1962 reviews of
Silent Spring. It is not always easy to be an environmental
pioneer challenging the status quo, but if your facts are
right you should eventually be accepted.
Delaware still has the extensive salt marshes needed to
support one of the largest shorebird migrations on the con-
tinent, largely because of the work of one man, former gov-
ernor Russell Peterson, and the Coastal Zone Management
Act that he convinced the legislature to pass. The act still
stands and works after many years, despite repeated attacks
on it by people who would like to industrialize the area.
The Earth Day started by Gaylord Nelson is observed each
year.
The number of schools including environmental educa-
tion in their curricula is increasing, although not as fast as
desired.14 In some cases student environmental groups
have prodded sluggish administrators into launching envi-
ronmental projects that saved the colleges significant
amounts of money.15
If people think through their causes carefully and ex-
plain them to their elected officials on a local, state, or na-
tional scale, good legislation may result that corrects a
problem. Calling the problem to the attention of others
through letters to the editor and op-ed pieces may encour-
age others to join the cause and contact their legislators
also. If you encourage candidates for office to explain their
positions and then vote carefully, you may also be able to
encourage the correction of problems. Unfortunately, too
many voters make their decisions on the incomplete data
given on television news, without understanding the full
situation. Individuals have sometimes been able to influ-
ence corporations to do better with less pollution by buying
some stock, then putting a proposal on the ballot for the an-
nual shareholders meeting. Although most such proposals
fail, the threat of a confrontation at the annual meeting may
sometimes force the company to adopt the proposal.16 The
Interfaith Center for Corporate Responsibility of New
York City pioneered this approach. It submits 80 or more
resolutions a year. Individuals can also help monitor the
health of local streams in Stream Watch programs. If the
stream’s health seems to be declining, it can be called to the
attention of the local authorities, who will see if anyone up-
stream is violating a discharge permit.
III. NONGOVERNMENTAL
ORGANIZATIONS
Individuals can also join environmental organizations that
can carry out detailed studies of problems and propose pos-
sible solutions to them. The organization may also function
as an alerting service on pending legislation, and such. One
520
of the oldest is the Sierra Club, which played a role in the
establishment of the national park and national monument
system in the United States.17 One of the world’s largest
environmental organizations, The Nature Conservancy,
was founded in the 1950s by a group of ecologists from the
Ecologists Union (which had split from the Ecological So-
ciety of America in 1946) for the purpose of preserving
species.18 Its program is laid out by scientists and imple-
mented in a nonconfrontational manner. Its staff consists
not only of ecologists, but also of realtors and tax special-
ists who help in the acquisition of land. In contrast, the
much smaller Earth First (founded in 1980) often engages
in dramatic, and sometimes violent, confrontational civil
disobedience. Greenpeace also uses the dramatic con-
frontational approach.19 An example is the use of a small
boat to try to prevent the dumping of toxic wastes into the
ocean. This attracts the attention of the media, which can
bring the problem before millions of people who may have
been unaware of it. Such tactics were successful in pre-
venting the sinking of an oil storage buoy in the North Sea,
the cheapest option for Shell, which owned the buoy.
Greenpeace feared that this would contaminate the sea. The
buoy was towed to shore for dismantling, and, hopefully,
recycling of the materials in it. Greenpeace was also in-
strumental in placing hydrocarbon refrigerants into Euro-
pean refrigerators to replace chlorofluorocarbons (CFCs).
Environmental Defense and the Natural Resources De-
fense Council consist of lawyers supplemented by staffs of
scientists. They defend the environment by bringing law-
suits under existing laws. For example, a project that would
destroy old-growth forest or wetlands may not have been
thought out carefully. They can ask the court to delay the
project until an environmental impact statement has been
prepared and submitted. These groups also propose new
legislation and devise new economic instruments for the
control of polluting activities. California’s Proposition 65,
which requires that consumer products containing carcino-
gens must list them on the label, is such a law. This law has
prompted many manufacturers to reformulate their prod-
ucts to remove the carcinogens. Occasionally, the organi-
zations work with industries to find solutions to prob-
lems.20 Environmental Defense has asked the 100 largest
chemical companies in the United States to run basic toxi-
city tests on the 71% of the 3000 chemicals used in largest
volume in the United States for which the data are lack-
ing.21 As of January 1998, 11 had agreed to do it, and 6 had
declined to do it. The American Chemistry Council (for-
merly the Chemical Manufacturers Association) and the U.
S. Environmental Protection Agency (EPA) had worked
out an agreement for the testing by 1999.
The Center for Science in the Public Interest, founded in
1971, has focused on improving the nutritional status of the
Chapter 18
food that Americans eat.22 Among its successes is the ban
on the use of sulfites (to which some people are sensitive)
on produce. Its newsletter, Nutrition Action, has 800,000
subscriptions.
Membership in environmental organizations, such as
The Nature Conservancy and the World Wildlife Fund, has
grown steadily over the years.23 The former had 1 million
members is 1999.24 Greenpeace peaked in 1990 with 2.35
million members. Some others have had rising and falling
membership, depending on what confidence people have
had in the government administration in Washington, D. C.
at varying times. It is the middle class that makes up most
of the membership. Members of Friends of the Earth in
England were 74% from the middle class. Professional or
technical people made up 48% of the membership.
National environmental organizations frequently oper-
ate by “mail order.” They buy mailing lists, and they try to
target the most likely prospective members. The mailings
can shape concern for tropical rain forests, whales, and oth-
ers. They may exaggerate the extent of the crises, and they
must propose solutions. Pictures of wildlife covered with
oil from a spill can motivate people. Some organizations
seem to have a monthly crisis that they use in trying to so-
licit additional funds from members.
Not everyone appreciates the efforts of environmental
groups. The Environmental Working Group put together
the data from the Toxic Release Inventory under the title of
Dishonorable Discharge: Toxic Pollution of America’s
Waters. One reporter wrote this up under the title, Infor-
mation Can Be Quite Uninformative,25 and proceeded to
ridicule the originators. Readers were quick to point out
that the thesis of the report did have some merit and should
not have been written up in this way.26 One pointed out that
the next page in the magazine covered the rising levels of
unexplainable deformities in frogs, which may turn out to
be related to what substances are dumped into lakes and
streams.
Not all environmental groups take the positions advo-
cated by modern science. Jeremy Rifkin of The Foundation
on Economic Trends has been described as a man “who’s
never met an engineered gene he liked.”27 (The value of
such genes was described in Chap. 9.) There are also orga-
nizations whose names make them sound as if they are
proenvironment, but that are set up to prevent environmen-
tal improvement. The National Wetlands Coalition (which
uses a symbol of a duck flying over a swamp) was set up by
a group of oil and gas companies, together with real estate
developers, to ease restrictions on converting wetlands to
drilling sites and shopping malls.28 Keep America Beauti-
ful was founded by the bottling industry to organize antilit-
ter campaigns. Its sponsors fight every new deposit–refund
legislation that is proposed. Consumer Alert was set up to
Greening
fight any new regulations relating to consumer safety. The
Council for Responsible Nutrition is a group of manufac-
turers of dietary supplements the purpose of which is to
prevent regulation of their products as foods by the U. S.
Food and Drug Administration.29
There has also been some backlash to the environmen-
tal movement.30 It is apparent from the letters to the editor
of Chemical Engineering News on the subject that at least
some chemists are not in sympathy with the environmental
movement. The ecologists, Anne and Paul Ehrlich, have
written a rebuttal to three such books pointing out inaccu-
racies and misstatements.31 Another book describes the
“environmentalist’s extreme, sensationalist view” of toxic
chemicals in the environment.32 The author feels that Silent
Spring is a polemic filled with alarmist statements. She is
employed by the American Council on Science and Health,
an industry-sponsored organization. Green Watch is a
twice-monthly newsletter covering the activities of envi-
ronmental groups.33 Its advertisement seeking subscrip-
tions says.
You should know what environmental activists
are plotting and how they could severely damage
your reputation and profits this year. New hidden
threats may be targeting the environmental policies
of your company, your industry, your association or
your clients.
IV. GOVERNMENT
Governments are supposed to take the long view that will
do the most good for the greatest number of people in the
long term. Ecopolitics leading to a green, sustainable soci-
ety should be part of this.34 This trend seemed to be true
from 1970 up to 1995 with the passage of numerous envi-
ronmental laws in the United States. The air and water of
the country became cleaner during this period. Then the
antienvironmental backlash hit as the 104th Congress con-
vened in 1995. This proved to be the worst congress on en-
vironmental matters in 25 years, as rated by the League of
Conversation Voters.35 With a maximum score of 100, 111
representatives and 24 senators received zeros. It was an
environmental backslide36 as efforts were made to weaken
major environmental laws and cut funding for renewable
energy studies, the Environmental Protection Agency, na-
tional parks, and others in the name of “regulatory reform,”
removal of “burdensome regulations,” and “balancing the
budget.”37 A number of the attempts showed up as riders
on unrelated appropriation bills, presumably to avoid floor
debate and with the hope that they would pass because
other congressmen would not want to delay an important
521
appropriations bill. This happened despite the overwhelm-
ing support of the public for strong environmental and pub-
lic health standards. That the efforts failed in large part was
probably due to this public which made its feelings known
to the congress and to the administration. The administra-
tion included the staunch environmentalist, vice president
Al Gore.38 The Office of Technology Assessment, which
won praise from many people for its reports over 23 years,
was a casualty of the 104th Congress.39
The American public had greened over the years, but
many of the special interest groups had not. Part of the
problem with the 104th Congress was the power of cam-
paign contributions. It takes a lot of money to run for
election to congress. Congressmen had voted three out of
four times for bills (to relax federal environmental protec-
tion) that were supported by groups that had given them
money through political action committees.40 These
groups included agribusiness, chemical manufacturers,
and natural resource extraction companies. Many chemi-
cal companies, as well as the American Chemistry Coun-
cil, also give “soft” money to the major political parties.41
Many congressmen were still not green in 1999. The U. S.
House of Representatives passed the Mandates Informa-
tion Act (H. R. 350) which requires estimates by the Con-
gressional Budget Office of the costs imposed on the pri-
vate sector by a regulation, but requires no estimates of its
benefits.42
Delaware has cleaned up 12 Superfund sites (out of the
20 most-polluted sites in the state) to the point that they are
virtually free of toxins.43 About 445 had been cleaned up
nationwide by August 1997. The Delaware Department of
Natural Resources and Environmental Control has shown a
willingness to work with polluters who violate their dis-
charge permits to help them clean up.44 The department
feels that this is better approach than the use of fines, but
this approach is not supported by some local environmen-
tal groups. The compliance rate for the period
1995–September 1996 was 99%, with an average of only
63 violations per month. The department points out that
runoff from roads, parking lots, overfertilized yards, and
farms produced ten times more pollution than that from the
75 permitted discharge pipes.
Europe has greened as well over the years. The Green
Party in Germany has been active. One result is the system
making manufacturers responsible for the disposal of what
they produce at the end of its useful life. Several countries
in Europe are incorporating ecotaxes into their tax systems,
as described in Chap. 17. Thirteen countries in Europe have
achieved zero population growth. Most companies in the
United Kingdom do not find environmental laws too oner-
ous.45 The European Union has greened more in some
ways than the United States, so that there have been con-
522
flicts over climate change, genetically engineered crops,
and the use of hormones in raising beef.46
Under the guidance of the United Nations, more and
more attention is being given to the earth’s environmental
problems,47 including that of environmentally sustainable
development. Many international conferences sponsored
by the United Nations have dealt with world problems. The
nations of the world have frequently recognized the prob-
lems. Actions taken (Montreal Protocol of 1987) have been
effective in the phase-out of the chlorofluorocarbons that
threaten the ozone layer.48 The 1997 conference, in Kyoto,
Japan, made a start in mitigating global warming (i.e., if the
nations can actually implement the reductions of green-
house gases agreed on). In other instances, the promise of
improvement remains largely unfulfilled.49 Ten years after
the Brundtland report50 on the need for a sustainable future
and 5 years after the Earth Summit at Rio de Janeiro51 most
of the problems identified were still there in 1997 or had
worsened. There have also been some problems in per-
suading some countries to comply with the treaties, such as
the Convention on International Trade in Endangered
Species and the ban on CFCs.52 The United States is trying
to eliminate a black market in CFCs.53
Nongovernmental organizations (NGOs) can send ob-
servers, but not delegates, to these international confer-
ences. Despite this second-rate status, they have influenced
the process of sustainable development.54 While at confer-
ences, they can disseminate information and offer new
ideas and suggestions. The idea of sustainable development
has become part of mainstream thinking, much more so
than 20 years ago.
International lending organizations have been criticized
by environmental groups for supporting projects that dam-
age the environment. Pressure from environmental NGOs
is forcing them to change. The U. S. Agency for Interna-
tional Development has changed the most, to the point that
it focuses on sustainable forms of development and even
supports biodiversity projects.55 The World Bank has made
less progress, but has changed and is still changing.56 Its
initial claims (1994) for a change to a “green agenda” were
viewed with skepticism by environmental groups. It funds
projects using fossil fuels that emit much more carbon
dioxide than the alternative energy projects that it funds.57
It cut back its family-planning aid in 1996.58 In 1998, it
wanted to lift its 1991 ban on investments in logging pri-
mary tropical forests.59 There have been complaints that
the power of its inspection panel has been weakened.60 In
1996, it had 200 environmental specialists in its staff of
11,000. Robert Goodland of the World Bank is in the fore-
front of environmental economics.61 The International
Monetary Fund62 lends money to countries that have prob-
lems with balance of payments. In return, it expects the
Chapter 18
country to show fiscal austerity. This structural adjustment
lending is exempt from environmental assessments. The re-
sult can be excessive exportation of natural resources to the
detriment of the environment. It is said to have greened the
least of the three lending agencies.
The World Trade Organization settles disputes among
nations when their individual trade laws conflict. There are
complaints that international trade is winning out over the
environment in some of the decisions. For example, it ruled
in 1998 that a U. S. law requiring turtle excluder devices to
protect endangered species of sea turtles from being
trapped in the nets of shrimp fishermen was really a trade
barrier and need not be enforced.63
V. CORPORATIONS
Many businesses have become greener since the founding
of the U. S. Environmental Protection Agency in 197064
and some more than others.65 R. E. Chandler of Monsanto
describes the response of the chemical industry to environ-
mentalism as consisting of three overlapping stages.66 The
first phase was the denial phase. Industry tended to deny
that major problems existed. It often predicted dramatically
high costs, job losses, and plant closures if the regulations
were enforced. This exaggeration caused it to lose credibil-
ity with both legislators and the general public. The second
phase was the “risk–benefit” one. Major U. S. chemical
companies launched expensive public relations campaigns
to convince the public that its emotions and fears of the un-
known should be replaced by a more industry-like view of
facts and reason in which the risk was small. Monsanto’s
Chemical Facts of Life of the late 1970s and early 1980s
was such a program. The third phase involves the “public
right to know,” which may have been a reaction to the dis-
aster at Bhopal, India. It includes a proactive openness with
the community. The goal is to go beyond compliance with
all laws to reduce all toxic and hazardous emissions, ulti-
mately to zero. This phase incorporates pollution preven-
tion. Some companies view environmental concerns as
profit-drivers (i.e., through higher sales of cleaner prod-
ucts). The actions of the 104th Congress in the United
States suggest that there are many companies that are still
in the first phase.
Another author describes the first phase as an inherently
defensive one, where management believes that it is being
treated unjustly by the regulatory authority.67 The third
stage is one during which there is a sustainable, interactive
program of environmental management within the com-
pany. Another author classifies corporations as red, yellow,
or green, depending on the extent of their conversion to a
long-term, opportunity-seeking, company-wide, cradle-to-
Greening
grave performance system, which is the green one.68 He
and others feel that the green phase should offer a compet-
itive advantage69 and be part of a sustainable future.70
It is possible that the companies that grumble the most
about environmental regulations are still in the first phase.
It is said that, “No major piece of environmental legislation
has ever been supported by corporate America.”71 A few
examples will illustrate the complaining often coming from
companies, or trade association that represent them. The
extent of the complaining may go up as the cost of compli-
ance becomes high, or as the amount of change required to
comply becomes large. Earnest W. Deavenport, Jr. of East-
man Chemical and the American Chemistry Council have
pushed for regulatory reform.72 An analysis sponsored by
Pfizer concluded that the laws disregard reality, that the
regulatory framework is impossible to administer properly
and that they foster excessive litigation.73 The U. S. Envi-
ronmental Protection Agency which administers the laws
enacted by the U. S. Congress is subjected to a lot of criti-
cism. Its expansion of the number of chemicals to be re-
ported in the Toxic Release Inventory was objected to by
the National Council of Chemical Distributors (which has
333 members).74 The American Petroleum Institute, repre-
senting refinery operators, says the cost of the new rule for
reducing the emission of toxic chemicals from refineries
will exceed the benefit.75 The reduction would be 227,000
tons annually. It also objects to the proposed reduction of
sulfur in gasoline.76 The National Association of Manufac-
turers says that “There are some serious problems with our
environmental regulatory system.”77 The association did
find that over half of the members that voluntarily changed
manufacturing processes to reduce waste or emissions
saved money as a result. Industrial groups have fought the
“credible evidence rule” which says that any evidence
deemed credible can be used to determine whether a facil-
ity is violating emissions standards.78 Electrical utilities
have sued the EPA over a rule that would reduce the emis-
sion of nitrogen oxides by 900,000 tons/r yr.79
The new standards for ozone (0.08 ppm) and small par-
ticulates are expected to prevent 15,000–20,000 premature
deaths and as many as 350,000 cases of aggravated asthma
each year80 (see also Chap. 17.). They are supported by the
American Lung Association and other environmental
groups. They have been opposed by the American Truck-
ing Association, the U. S. Chamber of Commerce, the Na-
tional Association of Manufacturers, the Chemical Manu-
facturers Association, the Air Quality Standards
Association (a group of electric power generators, oil com-
panies, and vehicle manufacturers), the Synthetic Organic
Chemical Manufacturers Association, and the National
Coalition of Petroleum Retailers.81 Opponents of the rule
say that the cost of compliance would cripple them. The
523
EPA estimates the annual cost of compliance at 6.5–8.5 bil-
lion dollars; the Reason Foundation (an industry-supported
think tank in Los Angeles) at 90–150 billion dollars ($250
per capita).82 S. Buccino of the Natural Resources Defense
Council pointed out that past estimates of the cost of air
quality improvements have been high.83 In 1970 Lee la-
cocca predicted that the Clean Air Act “could prevent con-
tinued production of automobiles.” In the 1980s, utilities
predicted the cost of control of acid rain at $1500/ton NOx,
yet the cost of a credit to emit a ton today is 100 dollars.
The oil companies predicted the cost of cleaner gasoline
would be up to $0.25/gal. It turned out to be only
$0.03–0.05/gal more. The Global Climate Coalition (a lob-
bying group for coal, oil, auto, and chemical industries) and
the Chemical Manufacturers Association have predicted
severe economic impacts as a result of the Kyoto agree-
ment by which the United States must reduce its emissions
of greenhouse emissions below 1990 levels.84 The coali-
tion predicts unemployment levels not seen since the Great
Depression. The coalition has also attacked the science be-
hind global warming.85 Environmental groups predict no
additional cost, because the cost of energy efficiency will
be offset by the savings from not having to purchase as
much energy. Because energy efficiency and renewable
energy are more labor-intensive than current oil and car
production, jobs may have to change, but there will be lit-
tle, if any, loss. A Business Roundtable (a group of top cor-
porate executives) study predicted job losses of 200,000–2
million from the 1990 amendments to the Clean Air Act.86
The actual number, as of June 1994, was 2363.
Many U. S. industries are becoming greener based on
what they say at meetings and in print.87 However, it is not
possible to tell how green they are by reading their annual
environmental reports.88 The level of disclosure is said to
vary greatly. There is a high degree of subjectivity and se-
lectivity in what is reported, often with a lack of quantifi-
cation of environmental impacts. A survey of 54 large U. S.
corporations, which expressed environmental concern
through such reports, found that only one-third of the com-
panies would switch to a less toxic material if it added 1%
to the cost of the product, but only two said they would be
willing to raise the cost 5%.89 Public relations firms can be
hired to write such reports, as well as prepare advertise-
ments, and even provide “citizen” letter-writing cam-
paigns.90 The advertisements may picture green forests and
wildlife next to the plant. At the same time, the company,
through its membership in a trade association, may be lob-
bying Congress to relax the laws that regulate it. One report
says that businesses in Great Britain are paying little more
than lip service to the environment.91
Advertising is big business. In 1989, its cost was 120 dol-
lars for every person in the world. The average child in the
524
United States sees 20,000 commercials in a year, each with
the message, “Buy this.”92 This is one cause of the over-
consumption in the developed nations. Corporations are
also flooding the schools with teaching aids and study
materials that may contain information that is misleading
or inaccurate, as well as advertising.93 The U. S. Environ-
mental Protection Agency suggests caution in accepting
“green” advertising claims. Its suggestions include look-
ing for claims that are specific, being wary of claims that
are overly broad or vague, realizing that many materials do
not degrade in landfills, or elsewhere.94 The sign on the bot-
tom of the six-pack of Coors beer says, “Do not litter high-
ways or public grounds. Keep our country beautiful.” The
consumer would be much more likely to see this message if
it were on the side of the six-pack holder instead of on the
bottom.
The Chemical Manufacturers Association (CMA) (now
the American Chemistry Council) was 125 years old in
1997. Its over 190 member companies make over 90% of
the chemicals that are produced in the United States.95 Its
future involves embracing sustainable development, estab-
lishing a health and environmental research program and in
bringing greater flexibility to government regulations.96 It is
collaborating with the U. S. Environmental Protection
Agency in the testing of high-volume chemicals for toxicity
and as endocrine disruptors.97 (The Synthetic Organic
Chemical Manufacturers Association objects to the “de-
sign” of the program, fearing that the cost of testing will be
a hardship on its members.98 It also criticizes the U. S. En-
vironmental Protection Agency for ignoring the “unique
needs of small-batch and custom chemical producers” and
“its opposition to promising suggestions”.99) The Chemical
Industry Institute of Toxicology is funded by the CMA.100
The CMA is proud of the record of the chemical industry in
reducing releases of chemicals on the Toxics Release In-
ventory more than 60% in 6 years.101 However, it opposed
expansion of the Toxics Release Inventory in the courts,
losing its suit in the appeals court.102 Its request to have
ethylene glycol removed from the Inventory was denied by
the EPA.103 It does not support additional testing of the
health effects of biphenyl, carbonyl sulfide, chlorobenzene,
ethylene glycol, methylisobutylketone, phenol, and
trichlorobenzene, as suggested by the EPA.104 It also op-
poses mandatory reporting of toxic chemical use, although
such systems appear to be working well in Massachusetts
and New Jersey105 (see also Chap. 17). The Synthetic Or-
ganic Chemical Manufacturers Association also objects to
this.106 Such inventory reporting should offer a maximum
of flexibility for those companies who dislike “command-
and-control” regulation. The Toxics Release Inventory re-
quires no reduction in emissions at all, but companies often
choose to make reductions after they realize how much they
Chapter 18
are losing in material and dollars.107 They may also be mo-
tivated by wanting a good public image. The American
Chemistry Council has spent 40 million dollars over 5 years
on an advertising campaign to create a better public image
for the chemical industry, but has discontinued the cam-
paign as a result of its failure to change public attitudes.108
The showpiece of the Chemical Manufacturers Associ-
ation is its “Responsible Care” program.109 The program
originated in Canada in 1985 and was adopted by the
American Chemistry Council in 1988. It has spread to
South America, Europe, Africa, Asia,110 and Australia, and
is now in 40 countries. The British Chemical Distributors
and Traders Association is encouraging all of its members
to sign up for the program.111 Only 92 of its 117 members
have done so thus far. Companies pledge to adhere to ten
guiding principles:
1. Recognize and respond to community concerns.
2. Develop chemicals that are safe to make, trans-
port, use, and dispose of.
3. Give priorities to environmental, health, and
safety in planning products and processes.
4. Give information on chemical-related health and
safety hazards promptly to officials, workers, and
the public, and to recommend protective mea-
sures.
5. Advise customers on the safe use and handling of
products.
6. Operate plants in a way that protects the environ-
ment and the health and safety of workers and the
public.
7. Conduct research on environmental, health, and
safety aspects of products, processes, and waste.
8. Resolve problems created by the past handling and
disposal of hazardous materials.
9. Participate with government and others to create
responsible regulations to safeguard the commu-
nity, workplace, and the environment.
10. Offer assistance to others who produce, use, trans-
port, and dispose of chemicals.
Skeptics, who felt at first that the program was just a
public relations ploy, now consider it to be real and worth-
while. They do point out that it may be written too broadly
and that it may not be quantitative enough. The president of
the American Chemistry Council has said, “We are acutely
aware that the initiative loses credibility if we say one thing
with Responsible Care and say another thing when we deal
with Congress or the regulatory agencies.” Independent
third-party verification is starting to be used by some com-
panies.112 The United Nations Commission on Sustainable
Development plans to “examine voluntary initiatives and
agreements,” but the CMA does not want “a formal U. N.
Greening
mechanism to oversee these programs.”113 Efforts need to
be increased to bring labor into the program, for it has felt
left out.114 If this approach and similar ones prove work-
able and verifiable, this may be a good alternative to enact-
ment of further regulations.115
There are some remaining skeptics. The U. S. Public In-
terest Research Group Education Fund found that more
than 75% of CMA members were unable or unwilling to
answer seven questions about toxic chemical releases, ac-
cidents, and storage and transportation safety.116 Some sci-
entists doing research on the toxicities of industrial chemi-
cals have felt that industry has been overly secretive when
asked to provide data.117 Part of this may be due to the liti-
gious society of the United States. The Coalition for Effec-
tive Environmental Information (an industry group) and
the American Chemistry Council have been reluctant to
disclose the “worst-case scenarios” required under the
Clean Air Act’s 1990 amendments to the general public for
fear that it might help terrorists.118 The Working Group on
Community Right-to-Know (a coalition of 150 organiza-
tions) feels that public disclosure is the best way to mini-
mize risk.119 Public disclosure might provide a strong in-
centive for a company to replace its processes with greener
ones using less toxic chemicals. The public was openly
critical at a meeting in Texas to explain companies’ risk-
management plans.120 A way must be found to improve the
dialogue between chemical plants and the communities
around them.
In 1988, the Coalition for Environmentally Responsible
Economics (a group of investors and environmentalists)
put together a code (first called the Valdez Principles, now
the CERES Principles) for corporations to follow.121 It in-
cludes
1. Reducing releases into the biosphere and protect-
ing biodiversity.
2. Sustainable use of natural resources.
3. Minimizing waste and disposing of it properly.
4. Sustainable use of energy.
5. Minimizing environmental, health, and safety
risks to employees and the public.
6. Elimination of products that cause environmental
damage.
7. Correcting any damage that may have been caused
to people and to the environment.
8. Informing those involved of any potential hazards
in a timely fashion.
9. Environmental interests must be represented on
the Board of Directors.
10. An annual self-audit will be made public.
This code is broader than Responsible Care. It includes
the concept of a sustainable future and requires that a self-
525
audit be made public. Large companies have been slow to
embrace it. Management usually recommends a vote
against the many shareholder resolutions that propose it in
the proxies for the annual meetings (e.g., GE in 1993 and
Goodyear Tire and Rubber in 1996). Those that have
adopted it include Sun Company, General Motors,122 H. B.
Fuller, Polaroid, and Arizona Public Service.123
The International Organization for Standardization
(ISO) was formed in 1946 to facilitate standardization as a
means of promoting international trade. It is located in
Geneva, Switzerland. Its ISO 9000 series, which deals with
product quality, has become almost a requirement for com-
panies to do business.124 The series is being extended to an
ISO 14,000 series dealing with environmental manage-
ment.125 These standards will include formalization of cor-
porate policies and audits, evaluation of performance, la-
beling, and life cycle assessments. The standards will be
worldwide and will require mandatory third-party verifica-
tion. The goal is to support environmental protection in bal-
ance with socioeconomic needs. If these standards are
adopted as widely as the ISO 9000 series has been, they
may become a powerful force in cleaning up the environ-
ment. Companies buying the chemicals may insist that
their suppliers adhere to the principles. This may be espe-
cially helpful in nations that lack an effective regulatory
system.126
It is not easy to tell just how green a company is.127
Stock analysts do not consider environmental performance
a major factor in evaluating companies.70,128 The U. S. Na-
tional Academy of Engineering is developing methods to
do this.129 The Investor Responsibility Research Center
evaluates companies based on Superfund sites, spills, total
emissions, enforcement actions, and penalties.130 (Such
data can usually be obtained from state environmental de-
partments in the United States.) The Hamburg Environ-
mental Institute evaluated the environmental friendliness
of nearly 70 of the largest chemical and pharmaceutical
corporations in its annual Top 50 report.131 The top 10 were
deemed “proactive.” The rankings of the 7 U. S. corpora-
tions in this category in the report for 1995 were Johnson &
Johnson first, 3M third, Procter & Gamble fourth, Dow
fifth, Baxter International sixth, Bristol–Meyers Squibb
ninth, and duPont tenth. Henkel (Germany) was second,
Ciba–Geigy (Switzerland) seventh, and Unilever (Nether-
lands) eighth. Some of the rankings change with the year.
duPont was 27th in 1994. Unilever was 22th in 1994. Six
U.S. companies were among the 22 classified as “active,”
the next lower level. The remaining 18 companies were
classified as “reactive,” the next lower level or “passive,” a
still lower level. Monsanto was 19th in the report. The U.S.
firms classified as “passive” were Merck 43rd, Colgate–
Palmolive 47th, Occidental 48th, and GE plastics 49th. The
526
lowest ranking, “negative” was given to firms that could
not be ranked “due to insufficient communication of their
environmental performance.” Firms in this category in-
cluded American Home Products, Exxon Chemical, Pfizer,
Schering–Plough, Warner–Lambert, and Rhone–Poulenc.
Overall, companies were weakest when judged on the “sus-
tainability” of their products.
The Council on Economic Priorities (a New York non-
governmental organization) produces an annual list of the
worst polluters in the United States.132 These ratings are
based on toxic releases, regulatory compliance, waste,
clean-ups, and worker health and safety of more than 100
companies. The 1994 list included Union Carbide (which
had three times as many spills as the next worst competitor,
as well as a higher than average frequency of health and
safety violations), Exxon, Texaco, International Paper,
Southern Company, Westinghouse, Westvaco, and Max-
xam (unsustainable harvesting of redwood forests). The
1995 list included Formosa Plastics, Exxon, Maxxam, and
Southern Co. (industry’s top emitter of carbon dioxide).
Texaco, Union Carbide, Westinghouse, International Pa-
per, and Westvaco were not on the 1995 list. “Businesses
on the list call it biased, distorted or just plain wrong.”
Along with the list, the Council recommends ways that the
companies can improve.
Some companies that are not very green make the news.
Condea Vista was found guilty of “wanton and reckless
disregard of public safety” by a Louisiana jury for a leak of
1,2-dichloroethane over an 8-month period.133 Georgia Pa-
cific was fined for failure to install pollution control equip-
ment for volatile organic compounds at 11 of its plants in
the southeastern United States.134 Installation of the control
equipment will reduce emissions by 5000 tons/yr. A For-
mosa Plastics polyvinyl chloride plant in Texas has agreed
to try to implement a zero-discharge system for wastewater
to a bay rich in shrimp and oysters.135 This follows years of
lawsuits, environmental violations, and millions of dollars
of fines. A ship carrying about 3000 metric tons of mer-
cury-containing waste from a Formosa Plastics Taiwan
plant to Cambodia was sent back to Taiwan by the Cambo-
dian government.136 ICI was reprimanded by the Environ-
ment Agency of the British government for 1996 spills of
1,2-dichloroethane, vinylidene chloride, chloroform,
trichloroethylene, and naphtha.137 When a titanium tetra-
chloride leak caused a road to be closed and a spill of light
oil into an estuary occurred two weeks after ICI promised
to clean up its act, the Environment Agency shut down the
titanium dioxide plant. The U. S. Department of Justice has
taken Borden Chemical and Plastics to court in an effort to
force it to clean up groundwater contaminated with vinyl
chloride and 1,2-dichloroethane at its polyvinyl chloride
plant in Louisiana.138
Chapter 18
At the other extreme is 3M, which has saved 1.4 billion
dollars in its Pollution Prevention Pays campaign through
3450 projects in the period 1975–1991.139 Pioneer Hi-Bred
International developed a superior soybean for use as an
animal food by inserting a gene from a Brazil nut.140 When
company testing showed that humans allergic to Brazil nuts
would also be allergic to the soybean, it decided not to re-
lease the new plant. Even though the soybean was meant to
be fed to animals, there was a possibility of its getting into
food for humans.
Many companies appear to be somewhere between the
extremes of “proactive” and “reactive,” but the general di-
rection is toward becoming greener. In addition to the cri-
teria for judging companies already mentioned, there are
some for which the necessary information is difficult to ob-
tain. For example, it is hard to know what role a company
plays in an antienvironmental stand taken by a trade asso-
ciation that it belongs to. Companies have also been criti-
cized for being greener in things that are relatively inex-
pensive than in ones involving a lot of money, but that may
have more environmental impact. There is also a legitimate
debate about whether or not some company actions are
green or not. For example, a new insecticide that contami-
nated air and water less than its predecessors would be an
improvement, but not as much as less pesticide use through
integrated pest management (see Chap. 2 for more detail).
The records of a few companies will be given to illustrate
the range of greening. Some of these can be compared with
the ratings given in the foregoing by environmental organi-
zations. The two companies cited that make agricultural
chemicals have shown little interest in alternative agricul-
ture, just as the oil companies cited have shown little inter-
est in renewable energy.
Ashland Oil reerected an oil tank on the banks of the
Monongahela River some years ago. When filled with oil
in 1988, the tank ruptured suddenly so that about 1 million
gal of diesel oil sloshed over the dike meant to contain it
and went into the river, contaminating it for miles.141 Since
then, starting in 1989, Ashland has cosponsored The Ohio
River Sweep, an annual riverbank cleanup of trash. The
company’s refinery in Catlettsburg, Kentucky, was granted
an operating permit by the state in 1995, following two
decades of emissions violations caused by equipment mal-
functions and deficient operating procedures.142 The emis-
sions included sulfur dioxide and calcium oxide dust. Ash-
land has “made impressive progress toward excellence in
the areas of environment, health, and safety.”143 “It recog-
nizes its responsibility to protect and maintain the quality
of the environment.” It has reduced its toxic chemical re-
leases more than 52% since 1990. Through the Wildlife
Habitat Council (an industry group), the company has set
up three sites on its properties as wildlife areas. It also con-
Greening
tributes to The Nature Conservancy, The Appalachian Trail
Club, The American Trust, The Conservation Fund, and
the Izaak Walton League. It has held household hazardous
chemical waste collections for several years. Its service-
station-stores in Saint Paul, Minnesota, use polycarbonate
milk bottles that can be refilled 60 times. The company’s
service stations have facilities for collecting used motor oil
for recycling. Ashland Chemical was the first chemical
company to link its corporate Toxic Release Inventory, Su-
perfund, solid waste, and wastewater reports to the U. S.
Environmental Protection Agency’s Envirofacts data ware-
house, which makes them available to anyone with access
to the World Wide Web.144
Chevron had two oil spills and a release of silica–alu-
mina catalyst in 1991–1993.145 Its oil spills have been re-
duced 97% since 1989. Losses owing to fire in 1993 were
37 million dollars. Fines of 1.4 million dollars were paid in
1993. The company is adding double-hulled tankers to its
fleet as a way to reduce the possibility of oil spills.146 Since
1989, and up to 1994, it had contributed about 7 million
dollars “to hundreds of conservation, wildlife preservation
and environmental research and educational organiza-
tions.” The company has won awards for its work with
wildlife habitat in Wyoming, Colorado, and other
places.147 Environmental groups have accused it of green-
washing in its “People Do” and other advertising.148 They
claim that the company is frequently doing only what the
law requires, while at the same time its lobbyists (through
its membership in the American Petroleum Institute) are
trying to convince the Congress to weaken the laws.
Chevron’s chairman has called for regulatory reform be-
cause, “Our regulatory system does not have a principle
that says ‘enough is enough.”’ He says that the regulatory
process has grown “bloated on an unbalanced diet of zero-
risk thinking.”149 Company management recommended
that shareholders vote against shareholder proposals at the
annual meeting asking that the company not drill for oil in
the Arctic National Wildlife Refuge, that the company pub-
lish a report on the environmental and safety hazards for
communities surrounding its plants, and that the company
publish a report on the contribution of its products to global
warming, as well as efforts to moderate this.150
In the early days of the U. S. Environmental Protection
Agency, the agency asked permission to inspect a Dow
plant. When the company refused in 1978, the EPA in-
spected the plant by flying an airplane above it. Dow sued
the EPA for illegal search and seizure, but lost in a case that
reached the U. S. Supreme Court.151 Dow is a greener com-
pany today. It plans to reduce waste by 50%, losses from
spills and leaks by 90%, release of dioxins by 90%, and of
toxic chemicals by 75%, by the year 2005.152 Its president
describes the third wave of environmentalism which will
527
be led by industry, because it can link business reality and
environmental progress. (He says that the first wave was
driven by environmental groups and the second by the
command-and-control methods of government.) Accord-
ing to him, “Poor environmental, health and safety perfor-
mance represents a waste of precious resources.” David T.
Buzzelli, a vice president of Dow, cochaired the Presi-
dent’s Council on Sustainable Development.153 Dow re-
ceived a Presidential Green Chemistry Challenge Award
for the use of carbon dioxide in blowing polystyrene
foam.154 Its second entry was the use of microemulsions to
replace traditional organic solvents. However, the com-
pany is still pushing the use of methylene chloride,
trichloroethylene, and perchloroethylene in its advertis-
ing.155 As mentioned in Chap. 17, Dow’s Louisiana plant
has an effective pollution prevention program, but a plant
in La Porte, Texas, has not put in pollution prevention that
would save $1 million/yr. The opportunities identified for
the reduction of waste and emissions which save dollars at
its Midland, Michigan, plant are being implemented.156
Dow’s contributions to congressmen through its political
action committees have been more than double those of
duPont and Monsanto.157 Dow and Cargill are producing
poly(lactic acid) from starch, for use as a replacement for
some polymers that are based on petroleum.158
When Delaware’s bottle bill and Coastal Zone Manage-
ment Act were proposed in the 1970s, the duPont Company
testified against them in public hearings. Since then, the
company has become greener. Paul Tebo of duPont points
to the company’s Chattanooga, Tennessee, nylon plant
which now achieves a 99.8% yield of saleable products, a
Lycra process that recovers 99.95% of its spinning solvent,
a biodegradable oil for two-cycle engines, shipment of
neoprene rubber in a Surlyn bag that can be compounded
right into the rubber, and an herbicide plant in Java that has
close to zero emissions.159 According to him, “We’re say-
ing the reason we’re making all these changes is not just
that it is good for the environment, it’s good for business.”
The company is striving for zero emissions. duPont now
makes methyl isocyanate from N-methylformamide on de-
mand on site and no longer ships it (as discussed in Chap.
2). It also makes phosgene as needed, so that the amount on
site is small. This is described as an interim measure until
a good phosgene-free route to isocyanates can be devel-
oped. The company has affiliated with the Pew Center on
Global Climate Change which supports the Kyoto Protocol
for reduction of greenhouse gases.160
duPont’s former chairman, Edgar S. Woolard, said,
As long as environmental protection is in a special
category assigned to certain people instead of a part
of a mental checklist with which every person ap-
528
proaches every task, then our environmental accom-
plishments will remain reactive and corrective rather
than proactive and innovative.161
He also favored regulatory reform of the “current regula-
tory morass.”162 The company presents grants to groups
that protect open space and natural areas. It has put a con-
servation easement on its farm near Chestertown, Mary-
land.163 A new plant in Spain, where historic buildings
have been preserved and the grass is cut by rare or endan-
gered local breeds of cattle, horses, sheep, and donkeys, in-
stead of lawn mowers, has been described as a model for
environmental and community relations in Europe.164 The
company is not without its critics. The U. S. Environmen-
tal Protection Agency fined the company 1.89 million dol-
lars for mislabeling herbicides (for neglecting to state that
eye protection was needed while spraying).165 It settled for
38.5 million-dollar lawsuits concerning contamination of
land adjacent to its Pompton Lakes, New Jersey, plant with
lead and mercury.166 It has been sued over the release of a
cloud of fuming sulfuric acid at a plant in Kentucky in
1995.167 A Texas shrimper has asked duPont to use its re-
verse osmosis membranes to provide zero discharge from
its Victoria, Texas plant, to protect nearby shrimp beds.168
Environmentalists opposed a duPont proposal to strip-mine
titanium minerals adjacent to the Okefenokee National
Wildlife Refuge, for fear that mining would alter the
swamp’s ground and surface water levels.169 They also ob-
jected to the company drilling for oil in the Grand Stair-
case–Escalante National Monument in Utah.170
Exxon is famous for the 1989 oil spill from its tanker,
Valdez, in Alaska, which resulted in the largest environ-
mental fines in U. S. history.171 In the period 1990–1995, it
has spilled only 250 gal of oil.172 The release of toxic chem-
icals has declined over 50% since 1987. The release of
volatile organic compounds from chemical operations has
been reduced 50% since 1990. Hazardous waste disposal
has been reduced by 75% since 1990. “The company is com-
mitted to continuous efforts to improve environmental per-
formance throughout its activities.” The company has “de-
veloped procedures to prevent seismic activity during
periods of fish spawning.” The company provides financial
support for projects to save the jaguar and the tiger, as well
as for the Bermuda Biological Station for Research, the
Royal Society for Nature Conservation in the United King-
dom, and others. The company belongs to the American
Chemistry Council and the American Petroleum Institute.
The company’s environmental coordinator says, “Govern-
ment and private research programs cannot afford to con-
tinue the adversarial approaches taken in the past.”173 The
company is against the new EPA regulations for ozone and
fine particulates. It feels that, “The government is rushing to
Chapter 18
impose these extreme new measures based on questionable
science. While the benefits are uncertain, no one will escape
the enormous costs.”174 It takes a similar position on global
warming.175 “The debate over global warming has been
clouded by assertions based on incomplete and uncertain
science. . . . The public debate continues to be inaccurate, in-
complete and misleading. . . . The climate proposals an-
nounced by President Clinton on October 22 would reduce
the U. S. gross domestic product by more than $200 billion.”
Monsanto (which split into Monsanto and Solutia in
1997 and is now part of Pharmacia) has devised ways to
make isocyanates without the use of phosgene (see Chap.
2). It has also found a way to make p-phenylenediamine
antioxidants without the use of chlorine (see Chap. 3).
The company pledge of 1990 includes the reduction of all
toxic and hazardous releases and emissions, working to-
ward the ultimate goal of zero effect.176 It pledges also to
“work to achieve sustainable agriculture through new
technology and practices.” It has offered two 1 million-
dollar challenges to anyone who can help it find a cost-ef-
fective and commercially practical way to recover useful
chemicals from its wastewater, at the same time reducing
their effect on the environment. Both have been won by
SRI International.177 Monsanto also won a Presidential
Green Chemistry Challenge Award in 1996 for a new
method to make disodium iminodiacetate, an intermediate
in the synthesis of the herbicide glyphosate.178 The inter-
mediate is made by the copper-catalyzed dehydrogenation
of diethanolamine. The new route eliminates the use of
hydrogen cyanide and formaldehyde, as well as eliminat-
ing 1 kg of waste for every 7-kg product. This “zero-
waste” route gives a higher overall yield with fewer pro-
cess steps. The company has produced Alachlor, an
herbicide often found as a contaminant in groundwater,
since 1969.179 The company also markets insect-resistant
corn and cotton which incorporate genes for Bacillus
thuringiensis toxins, as well as cotton and soybeans that
are resistant to its herbicide glyphosate.180 Environmen-
talists are concerned about the rate of build-up of resis-
tance that will take place in insects and weeds (as men-
tioned in Chap. 11). There is also the question of the
extent of soil erosion with soil kept bare except for the
crop. Alternative agriculture could be a more sustainable
alternative.
Motiva Enterprises (called Star Enterprise before
Shell’s purchase of part of it in 1998) is a joint venture of
Texaco, Shell, and the Saudi Arabian Oil Company. Its op-
erations include a refinery, located near Delaware City,
Delaware, which has had difficulties in meeting environ-
mental standards over the years. (The following dates refer
to items from the Wilmington Delaware News Journal, ex-
cept as referenced otherwise.)
Greening
1/31/85: 19,000 gal of sulfuric acid spilled, contaminat-
ing Red Lion Creek
2/19/87: 60,000-dollar fine for emissions of sulfur diox-
ide
6/10/88: large emissions of carbon monoxide and coke
dust
9/26/89: 425,000-dollar fine for air pollution and mis-
handling of hazardous wastes
8/14/92: 1.68 million-dollar fine for discharging toxic
chemicals into the Delaware River
3/11/95: state of Delaware sues Star Enterprise for 19
odor violations since 9/16/94
4/12/95: odors attributed to a malfunctioning sulfur re-
covery unit—unmarked pipes misconnected, bypass-
ing wastewater treatment unit—suit claiming 120 vi-
olations of federal water rules in January 1994,
settled out of court for 360,000 dollars
6/8/96: blower failure bathes area homes in soot
6/11/96: odor problems with the sulfur recovery unit—
fined $175,000 dollars for odor problems from Sept
1994–Dec 1, 1995
7/2/96: odor problems due to starting operation without
a scrubber
6/11/97: state of Delaware permit “caps the amount of
sulfur that can be recovered and burned off during
processing”
9/10/97 and 9/12/97: U. S. EPA fines Star Enterprise
125,000 dollars for violating the Clean Water Act
10/31/97: power failure causes refinery to emit thick
black smoke
12/15/97: four employees treated for caustic burns at the
local hospital after an explosion
2/19/98: sulfur dioxide and carbon monoxide released
after a fire disables a pollution control system
4/22/98: fined 125,000 dollars for polluting the river be-
tween 1993 and 1997
7/7/98: sues the Delaware Department of Natural Re-
sources and Environmental Control to prevent re-
quired reductions in emissions of nitrogen oxides
7/12/98: fined 75,000 dollars for breaking a federal
court ban on new wastewater violations between
1995 and 1997
9/2/98: federal judge orders monitoring studies of the
damage that its pollution has caused to the Delaware
River
5/25/99: a federal appeals court upholds the decision of
the judge above181
1/8/00: crude oil fuels fireball at plant
5/21/00: flash fire injures an employee
The refinery has also maintained a productive natural
marsh on its property for many years. As mentioned
in Chap. 1, its toxic emissions are very small com-
529
pared with those emitted by automobiles in northern
New Castle County.
Texaco has had other problems as well:
The company paid fines of 2,807,375 dollars in 1992,
most of the fines being for an oil spill in Fairfax, Vir-
ginia.182
2/22/93: state of Washington fined the company 9.4 mil-
lion dollars for an oil spill.183
5/19/97: more than 10,000 gal of oil spilled from a rup-
tured pipeline in Louisiana.
Texaco ended operations in Ecuador in 1992. Oil spills
and overflowing waste pits had contaminated the
land and the drinking water. The company says that
it compiled with all rules in force at the time. It at-
tributes many of the spills to natural disasters. The
jury at the International Water Tribunal in Amster-
dam found that large quantities of hazardous waste
entered the soil and water with at most superficial
measures to minimize spills and contamination.184
3/26/97 and 1/4/97: Texaco settles racial discrimination
suit for 176 million dollars. The company has an-
nounced a comprehensive plan to promote employ-
ment and business opportunities for minorities.185
Texaco has supported the radio broadcasts of the
Metropolitan Opera for many years. The company has
made donations to the Marine Biological Laboratory in
Woods Hole, Massachusetts, the New York Botanical Gar-
den, Louisiana Nature and Science Center, and The Nature
Conservancy. It also supports an urban tree-planting pro-
gram.186 It donated 3000 acres of cypress–tupelo swamp in
Louisiana to the Nature Conservancy for a bird refuge in
1994.187 It has also donated 10,000 acres of land in Utah for
a wildlife habitat in 1995.188 The company also refers to
“continued cost-inefficient government regulations” in the
same report.
The president of Texaco stated in the “Environment,
Health, and Safety Review for 1992, “The drive to lead is
an intrinsic part of the Texaco way of life, and our work in
the areas of environment, health and safety is no excep-
tion.” In the corresponding report for 1996, the new chair-
man of the board said, “Excellence in environmental,
health and safety performance must be an integral part of
all our business operations.”
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126. Chem Eng News 1996; Jan 29:15.
127. J.W. Houck, O.F. Williams, eds. Is The Good Corporation
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128. A. Thayer. Chem Eng News 1998; May 4:31.
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130. V.N. Bhat. The Green Corporation—The Next Competi-
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131. M. Freemantle. Chem Eng News 1996; May 20:30.
132. (a) Chem Ind (Lond) 1994; 928; (b) Wilmington, Delaware
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133. Chem Ind (Lond) 1997; 855.
134. Chem Eng News 1996; July 29; 33.
135. (a) S. Ainsworth. Chem Eng News 1994; July 18:9; (b) J.F.
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138. Chem Eng News 1994; Nov 7:14.
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140. F. Krupp. EDF Lett (Environmental Defense Fund) 1996;
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141. (a) M.R. Lee. A Review of Oil Pollution Prevention Regu-
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142. W. Lepkowski. Chem Eng News 1995; July 10:7.
143. Ashland Inc, 1995 Annual Report on Environment, Health,
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144. Chem Eng News 1997; July 21:22.
145. Chevron. Measuring Progress—A Report on Chevron’s
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146. Chevron. 1997 Annual Report.
147. Chevron. Quarterly reports to shareholders for the third
quarters of 1996 and 1997.
148. (a) Earth Day 2000. The Don’t Be Fooled Report—the Top
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D. Helvarg. Amicus J 1996; 18(2):16.
149. Chevron. Report to shareholders for the second quarter of
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150. (a) Chevron. 1995 meeting report, June 10, 1995; (b)
Chevron. Report to shareholders, first quarter 1997; (c)
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151. E.N. Brandt. Growth Company—Dow Chemical’s First
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152. L. Raber. Chem Eng News 1996; May 6:7.
153. Chem Eng News 1996; Aug 19:13.
154. The Presidential Green Chemistry Challenge Awards Pro-
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155. Chem Eng News 1997; Mar 10:1.
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157. D. Fagin, M. Lavelle. Toxic Deception—How the Chemi-
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158. Chem Eng News 1997; Dec 1:7.
159. (a) J.H. Krieger. Chem Eng News 1996; July 8:13; (b)
Green Chemistry and Engineering Conference, Washing-
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28(3):8.
160. B. Hileman. Chem Eng News 1998; Nov 23:10.
161. S.J. Bennett, R.L. Freierman, S. George. Corporate Real-
ties and Environmental Truths—Strategies for Leading
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162. E.S. Woolard. Chem Ind (Lond) 1995; 436:969.
163. (a) M. Murray. Wilmington Delaware News Journal 1996;
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164. P.L. Layman. Chem Eng News 1999; Mar 29:16.
165. G. Parkinson. Chem Eng 1998; 105(7):31.
166. C. Aregood. Wilmington Delaware News Journal 1997;
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7:12.
168. (a) W. Lepkowski. Chem Eng News 1996; July 15:24; (b)
Environ Action 1996; 28(1–2):39.
169. (a) M. Reisch. Chem Eng News 1997; Apr 14:9; (b) A.M.
Thayer. Chem Eng News, 1998; Mar 9:10.
170. J. Gerstenzang. Wilmington Delaware News Journal 1997;
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171. Valdez Litigation Update. Exxon Perspectives (a quarterly
newsletter for shareholders), Sept 1996; 5.
172. Exxon. Environment, Health and Safety Progress Report
for 1995.
173. B. Hileman. Chem Eng News 1996; May 27: 27.
174. Exxon Perspectives (a quarterly newsletter to sharehold-
ers), Mar 1997.
175. L. Raymond, et al. Exxon Perspectives (a quarterly
newsletter to shareholders), Dec 1997.
176. R.E. Chandler. In: K. Martin, T.W. Bastock. Waste Min-
imisation—a Chemist’s Approach. R Soc Chem Cam-
bridge, 1994; 71.
177. (a) Chem Eng News 1994; Aug 29: 21; (b) G. Samdani.
Chem Eng 1995; 102(5):19; (c) Chem Ind (Lond) 1994;
668; (d) Chem Eng News 1995; Jan 9: 9; (e) Chem Eng
News 1996; Apr 8:36; (f) Chem Eng News 1996; July 22:
36. (g) E.R. Beaver. Environ Prog 1997; 16(3):F3.
178. The Presidential Green Chemistry Challenge Awards Pro-
gram—Summary of 1996 Award Entries and Recipients.
EPA744-K-96-001, U. S. Environmental Protection
Agency, Washington, DC, July 1996; 2.
179. D. Fagin, M. Lavelle. Toxic Deception; How the Chemi-
cal Industry Manipulates Science, Bends the Law and En-
dangers Your Health. Carol Publishing, Secaucus, NJ,
1996.
180. (a) A. Thayer. Chem Eng News 1997; Dec 22: 18; (b) M.S.
Reisch Chem Eng News 1998; Jan 12: 106.
181. Amicus J. 1999; 21(3):46.
182. Texaco Inc. Environment, Health and Safety Review,
1994; 13.
183. Chem Eng News 1993; Feb 22:14.
Chapter 18
184. (a) J. Kane. Savages. Knopf, New York, 1995; 190; (b) En-
vironment 1995; 37(1):21; (c) Texaco. Annual Report for
1994; 13; (d) Texaco. Annual Report for 1995; 22; (e) Re-
port on the 1995 annual meeting of Texaco, June 8, 1995;
(f) Texaco Inc. Environment, Health and Safety Review
1994; 21; (g) Texaco Inc. Environment, Health and Safety
Review 1996; 28.
185. (a) New York Times 1996; Dec 22:E8; (b) P.I. Bijur. Let-
ter, to shareholders, Nov, 16, 1996.
186. Texaco Inc. Environment, Health and Safety Review 1994;
22.
187. B. Anderson. Nat Conserv 1994; 44(2):30.
188. Texaco. Annual Report for 1995; 22.
189. (a) H. French, World Watch, 1999; 12(6):22. (b) C. Hogue,
Chem. Eng. News, Nov. 29, 1999; 24; Dec. 20, 1999; 19;
Jan. 17, 2000; 47.
RECOMMENDED READING
1. R.E. Chandler. In: K. Martin, T.W. Bastock Waste Minimisa-
tion: a Chemist’s Approach. R Soc Chem Cambridge, UK,
1994; 63 [stages of greening of companies].
2. J. Nash, J. Ehrenfeld. Environment 1996; 38(1):16 [voluntary
agreements for self-regulation].
3. D.C. Korten. When Corporations Rule the World. Kumarian
Press, West Hartford, CT, 1995; 329 [the June 12, 1992
“Proactive Agenda for the Future” adopted by NGOs at Rio
de Janeiro].
4. B. Hileman. Chem Eng News 1997; Dec 22:20 [Kyoto con-
ference on global warming].
EXERCISES
1. Pick a company in your geographic area and see
how green it is. Check its Toxic Release Inventory,
spills, Superfund sites, enforcement actions, penal-
ties, annual report, items about it in the local news-
paper, and what trade associations it belongs to, to-
gether with their actions. (If you cannot find all of
these, use what you can. If you are in a country
other than the United States, try to find comparable
data.)
2. See what N.G.O.’s are active where you live. What
do they do? How could they be more effective?
3. Consider the regulations in effect where you live.
Are there too many or too few? Are they effective?
How might they be improved? Have you discussed
them with your elected officials?
Index

Abnormal events, 9 Agriculture, alternative, 326

Abortifacients, 487 Agriculture, sustainable, 324, 348
Absorption refrigeration, 55, 452 Agrochemicals, 319
Accreditation systems, 507 problems with, 322
Acetic acid, manufacture from ethylene, 159 Air pollution, deaths from, 5
Acetonitrile, manufacture of, 150 Alcohols, dehydration with membranes, 188
Accidents oxidation of, 250
causes, 7–10 Aldehydes, asymmetric addition of organometallic compounds,
with chemicals, 6 310
cost of, 10, 11, 13, 504 by oxidation of alcohols, 80, 90–91
with flammable gases, 7 Aldol Reaction, 258
frequency and severity, 7 Aldolases, 249
human error in, 10 Algal blooms, 498
with nuclear energy, 7 Alkaloids, 293, 308–309
prevention of, 9–11, 13, 18 Alkylation
with sulfuric acid and sulfur trioxide, 10 of aniline, 213
Acid acceptors as stabilizers, 396 of aromatic compounds, 135, 137, 141, 147, 154, 158
Acid mine drainage, 443 in asymmetric synthesis, 302
Acid rain, 400, 444 of benzene, 205, 221
Acids (See also carboxylic acids), 135 in sc carbon dioxide, 211–212
Acids and bases, solid, 135–161 with dialkyl carbonates, 32
Accounting of isobutane with olefins, 135, 138, 147, 158
green, 501 in sc methanol, 213
antiquated systems of, 501 of phenols, 143
Acrylic acid, manufacture of, 363 in water, 214
Acrylamide, manufacture with enzymes, 255 Alkylphenols as hormone mimics, 49
Acylation Alkynes, reduction of, 121
of alcohols and aromatic rings, 139, 141, 154 Allelopathy, 340
with zeolites, 148–149 Alternative agriculture, 326
Adhesives, 227 Alternative medicine, 5
for repulpable paper, 413 Alumina supports, reactions on, 103
Adipic acid, enzymatic preparation from maize, 259 Aluminum, perfluorocarbons made in manufacture of, 54
from glucose, 366 Aluminum phosphates, 146
by oxidation of cyclohexene, 84 American Chemistry Council, 6, 50, 510, 520–521, 523–525
from petroselenic acid, 365 Ames test, 3, 445
Advertising and consumption, 433 Amides, preparation with enzymes, 255
Advertising and greening, 523–524 Amines, polymeric, 115
Aflatoxin, 2 Amine oxides, use in oxidation, 69

535
536 Index

Ammonia, manufacture of, 325, 447 Banks, international, 522

Ammonium nitrate, explosions with, 9 Bankruptcies, 2
Amino acids, 293–294 Barrier coatings, 226
made by fermentation, 242 Bases, solid, 142–143
-Aminolevulinic acid for control of weeds, 341 Batteries
Androgens, 484, 489 ferrates in, 464
Aniline, alkylation of, 155, 213 lithium, 464
in oil, deaths from, 5 nickel-cadmium, 463
polymerization of, by peroxidase, 264 nickel-metal hydride, 463
Animal feeds, enzymes in, 263 recycling of, 68
Animal waste zinc-air, 464
pollution from, 344, 456 Baeyer-Villiger Oxidation, 84
reuse of, 344 Beckman rearrangement, 150
Anodes, sacrificial, to prevent corrosion, 399 Beneficial bacteria and fungi, 341–342,
Antiobiotic resistance genes in crops, 347 storage stability, 341
Antibiotics in animal feeds, 323 Beverage containers, 426–429
Antibodies, catalytic, 248, 301 poly(ethylene terephthalate), 429
in transgenic plants, 266 polycarbonate, 429
Antibody libraries made by combinatorial biochemistry, 118 reuse, 430
Anticancer agents, 269 Benzene, conversion to phenol, 92, 122
Antienvironmental organizations, 520 Bhopal, India, accident at, 7, 28
Antifeedants, 329–331 Biocatalysis
in marine organisms, 330–331 advantages and limitations, 241
Antifoulants, 71–72 at high concentrations, 245
Antiknock agents in gasoline, 74, 78 industrial products from, 242
Antimalarials, 267 substrates for, 242
Antioxidants, amine, 392 Biocides, 70
health, relation to, 4 Biocides, polymeric, 118
hindered phenols, 393 Biodegradable polymers, 419
natural, 4, 396–397 Biodesulfurization, 262
Aquaculture, 274, 326 Biodiesel fuel, 252, 257, 370, 456
Aromatic compounds made with enzymes, 259
Biodiversity, 267,
Arsenic, 65–66, 70
economic value of, 498
Asbestos, 65
Biofiltration, 262
replacements for, 92
Biofinishing of textiles, 261
Ascorbic acid, 259
Biogas, 344, 456
Asphalt, made with used rubber tires, 421
Biological control
Asymmetric autocatalysis, 310
of insects, 328
Asymmetric oxidation, 306–309
of plant and animal pathogens, 341
Asymmetric reduction, 302
Biomass, energy from, 457
by boranes, 302–303
Biomining, 261
catalytic with hydrogen, 304
Biphasic reactions, 16, 173, 175
by microbes, 302
Bioremediation, 262
Asymmetric synthesis, 301–314
BINAP, 304
Atrazine, 324
Automobile finishes, 227 Binaphthols, preparation of, 82
Automobile recycling, 422 BINOL, 304–307, 310, 312
Azo dyes, 73 Bird feathers, colors of, 73
Bird repellent, 331
Bacillius thuringiensis toxin genes in crop plants, 266 Bisoxazoline ligands, 311–312
effects on non-target species, 328–329 Bisphenol A
Backbiting in oxidation of polymers, 392 manufacture of, 113
Bacteriocides, polymeric, 118 toxicity of, 50
Baculoviruses, 328 Bleaching paper
Bagasse, paper made from, 415 with chlorine, byproducts of, 50
Ball mills, reaction in, 207 without chlorine, 50
Band gaps, 461 Blowing agents, 52
Index 537

Borohydrides, polymeric, 114 Carboxylic acids

Boronic acids for separating sugars, 181 enzymatic reduction of, 251
Bottles, saving money with refillable, 504 manufacture by fermentation, 242, 254
Bromofluoro compounds, 54 separation by amines, 176
Buildings, disassembly of, 424 Carcinogens in food, 4
1,3-Butadiene, manufacture of, 362 Car painting, 227
1-Butene, manufacture of, 362 Catalysts
1,4-Butanediol, manufacture of, 364 containing heavy metals, 72
tert-Butyl methyl ether, 78, 175 development by combinatorial chemistry, 118
in groundwater, 445 encapsulation in silica, 78
preparation with heteropolyacid catalyst heterogeneous, deactivation of, 102
Butyl rubber, preparation without chlorinated solvents, 56 model compounds for, 110
Butyraldehyde, byproducts of manufacture, 16 recovery of, 13
Byproduct use, 15 spent, recovery of metals in, 73
spent, metal reuse in fertilizer, 13
Cadmium, 65–66, 75–76
water-soluble, 216–217
Calcium carbonate for storage of heat, 453
Catalytic membrane reactors for dehydrogenations, 188
Calcium oxide, 143
Catalytic antibodies, 248
Calcium sulfate from waste, 15
Catechol, 369
Calixarenes, 180–181
enzymatic preparation of, 250
Campaign contributions, 521
Cell cultures, 274–275
Cancer, relation of lifestyle to, 4
Cellulases, 261
“Cap and trade” systems, 508
Cellulose, 372
Caprolactam, manufacture of, 87, 139, 150
derivatives made in extruders, 373
Carbamate insecticides, 28
esters and ethers, 373
Carbamates
regenerated to make rayon, 18, 372
from dialkyl carbonates, 29–30
preparation, 29–36 Ceramics, strengthening of, 398
Carbodimides, 38 CERES principles, 525
Carbonates, manufacture of, 31 Charge transfer complexes as inclusion compounds, 179
Carbon dioxide Chelating agents
use in alkylation of isobutane with butanes, 147 for metal ions, 69
for drying of gels, 138 on silica, 107
for dyeing, 74, 213 Chelating ion exchange resins, 113
emissions of, 449 Chemical defenses of plants and animals, 267
for enzymatic reactions, 213 Chemical Manufacturers Association (See American Chemistry
for extractions, 210, 213 Council.)
for fractionations, 210 Chemical vapor deposition of metal coatings, 76
for hydrogenations, 212 Chemicals, hazardous, used in manufacturing, 6
use in impregnation of polymers, 211 Chemophobia, 2
for making artificial bone, 213 Chernobyl, accident in nuclear reactor, 7
for making powder coatings, 213 Children, effect of chemicals on, 6
microemulsions with water, 213 Chiral
photochemical reactions in, 212 auxiliaries, 302
polymerizations in, 211 bases, 312
use in preparation of dialkyl carbonates, 31 catalysts, polymeric, 313
use in preparation of isocyanates, 33 columns, 297
use in preparation of microparticles, 211 Lewis acids, 310
reactions in, 210–214 ligands, 304–314
for removal of photoresists, 213 phase transfer catalysts, 312
for recycling of alkali metal ions, 176 phosphines, 304–305
sequestration of, 449 pool, 292
for spray painting, 213 Chitin and chitosan, 374
surfactants for, 211 Chloroacnegens, 49
Carbon membranes, 186–187 Chlorine-containing
Carbon monoxide, use in preparation of isocyanates, 29, 32–35 chemicals, 45–47
Carbon tetrachloride as a reagent, 125 toxicity of, 48
538 Index

[Chlorine-containing] Companies, rated for greenness, 525

pesticides, replacement of, 58 Company arguments against environmental regulations,
raw materials, but no chlorine in the product, 56 527–528
solvents, 55 Company contributions to charitable organizations, 527–529
Chlorine and chlorine dioxide as biocides, 71 Compatibilizers for polymer blends, 416
Chlorine controversy, 45 Composites from waste paper, 414
Chlorine use, 45–47 Composting, 423
Chlorofluorocarbons (CFCs), 2, 52 Condoms, 487–489
for cleaning electronic parts, 53 Consumer choices, 518
disposal of, 54 Consumer testing groups, 519
use in making foams, 53 Consumption and affluence, 483
as propellants, 53 Coolants for cars, recycling of, 399
Chloroform, byproduct of the disinfection of water with Corporations, narrowness of business approaches, 505
chlorine, 51–52 Corrosion, 399
Cholesterol, removal with a cyclodextrin, 125 inhibition
Chromate corrosion inhibitors, 400 by amines, 400
Chromium, 65–67, 70, 72–73, 75–77, 80, 83 by chromate, 400
Chromium copper arsenate, 70 by films of metal oxides, 402
Clay by polymers, 401
catalysts, 154 resistant materials, 400–401
films of, 156 variables in, 399
ion exchange of, 154 Conservation biology, 271
pillaring of, 154–156 Conservation of natural biodiversity, 271
in polymers, 398 Containers
uses of, 154 for beverages, 428
Cleaning, 220 reuse of, 428
without chlorinated solvents, 55 Constant growth, myth of, 434
of electronic parts, 53 Consumption
elimination of the need by change of process, 53 reduction of, 432
Clothing reuse, 425 relation to advertising, 433
Coatings, 223–228 Contraceptives
for automobiles, 227 implanted, 486
diamond, 226 for males, 489
failures, 227 oral, 485–486
as oxygen barriers, 226 physical barrier, 487
from plasma, 226 relative effectiveness, 491
for poly(ethylene terephthalate), 226 relative use of, 492
powder, 224 vaccine, 491
radiation-cured, 225 Controlled release of agrochemicals, 321
scratch-resistant, 226 Copper, 65–67, 80
of silica made in plasmas, 226 Corporate greening, phases of, 522
of titanium dioxide, self-cleaning, 56 Crop rotation, 326
water-borne, 223 to control root pathogens, 341
Cobalt, 65–67 to control weeds, 339
Cockroach control, 338 Crop residues in compost, 327
Cofactors for enzymatic reactions, 249 Costs
Coil coating, 226 diffuse, 502
Colloidal metal clusters, 110 externalized, 502
Colors from thin films, 73 hidden, 501
Combinatorial chemistry, 116–118 of transportation, 446
analysis of products, 117 Cost-benefit analyses, 501
use of poly(ethylene glycol)-containing supports, 117 limitations of, 501
for preparation of catalysts, 118 Cotton, 372
for preparation of new materials, 118 genetic engineering of, 266
soluble supports in, 117 p-Cresol, manufacture from p-cymene, 368
Commodity chemicals from renewable raw materials, 361 Cross-linked enzyme crystals, 244, 246, 298
Index 539

Crown ethers 4-Dimethylaminopyridine, polymeric counterparts, 115

separations with, 181 Dimethyl carbonate
use with enzymes, 247 manufacture of, 31
Crytosporidum in water, 52 preparation from carbon dioxide, 31
Cumene, 147 Diols, inclusion compounds from, 178
Curcurbituril, 177 Dioxins, 48
Cutting oils, water-based, 399 removal from stack gases of incinerators and power plants, 58
Cutting tools, hard coatings for, 398 separation by zeolites, 152
Cyanide in electroplating, 76 from combustion of waste, 49
5-Cyanovaleramide, 256 Dioxiranes, as oxidizing agents, 89
Cyclodextrins, 124–126 Diphenolic acid, 366
guests in, 124 Diphenyl carbonate, 31, 39
as hydrotropes, 218 Directed evolution of enzymes and organisms, 247, 323
polymers containing, 126 Disease prevention, 4
preparation of polymers in, 125 Diseases, tropical, 2, 505
reactions in, 124 drug-resistant, 2
supported on silica, 126 Disinfection of water
in Wacker Reaction, 159 with chlorine, 51
Cyclohexane, oxidation of, 86, 89 with light and titanium dioxide, 52
with hydrogen peroxide and a heteropolyacid, 160 by oxidizing agents, 52
photochemical, 466 by physical means, 52
Cyclohexanone, preparation from cyclohexene, 159 Distillation, reactive, 147, 175
Cyclohexanone oxime, 87, 139, 150 District heating, 445
Cyclopentadiene, separation from C5 refinery stream, 175 Drug companies, reluctance to work on tropical diseases, 505
Drugs from plants and animals, 267
Dawson ions, 157 Dry cleaning without perchloroethylene, 56
Daylighting, 454 DuPont nylon intermediates and byproducts, 14–15
Deacon Process, 58 Dyeing in sc carbon dioxide, 74
Deactivation of catalysts, 102 Dyes, decolorization with hydrogen peroxide, 51
Deaths, preventable, 4 Dyes and pigments, 73
1-Decene, oligomerization of, 155 Dynamic resolution of racemates, 299
Deforestation, 271
Deinking paper, 411 Ecdysone, 334–335
flotation in, 412 Ecolabels, 431, 501
Delaney Clause, 3 in consumer choices, 505, 507, 509
Dendrimers as supports, 110 Ecological economics, 497
Deposit-refund systems, 432, 508 Ecological footprint, 499
Deracemization, 299 Economics of recycling, 432
Desulfurization Ecoparks, 432
of fuels, 262, 446 Ecosystem services, 497–498
of petroleum with hydrogen peroxide and heteropolyacids, Ecotaxes, 510
160 Ecotextiles, 73
Detergent alkylate, 135, 147 Ecotourism, to save nature, limitations of, 506
Detergents (See surfactants.) Electrically-assisted oxidations, 90
Devulcanization of rubber, 421 Electricity, generation of, 443
Diapers, life cycle analyses of, 500 Electrochemical oxidation and reduction, 465
Dialkyl carbonates, use in alkylations, 32 Electrochemical syntheses, 464
Diamond coatings, 226 to regenerate expensive or toxic reagents, 465
Diastereoisomeric resolution of racemates, 297 as clean technology, 466
DDT, 58, 319 Electrodialysis, 183
effect on birds, 1 to recover acids and bases from their salts, 183
2,4-Dichlorophenoxyacetic acid, 319 Electron beams, curing coatings with, 225–226
Diesel engine soot, mutagens in, 445 Electroplating, 75
Diet and health, 4 Electropolymerization, 224
Dietary supplements, 5 Electrowinning of metals, 69
Di(2-ethylhexyl) phthalate, toxicity of, 50 Elicitors for phytoalexins, 337
Dihydroxylation of olefins, 120, 308 Elicitors used in cell culture, 274–275
540 Index

Emissions, reduction of, 503 Ethyl alcohol (See ethanol)

Endangered species, 271 Ethylbenzene, 147–148, 175
Endemic plants and animals, 271–272 from renewable raw materials, 368
Energy from biomass, 457 Ethylene, preparation of, 362
Energy, efficiency standards for, 451 from methanol, 149
Energy, problems related to, 443 Ethylene glycol, toxicity of, 18
Energy storage, 463 Ethylene oxide, 363
batteries for, 463–464 Ethyl lactate, 189, 202
Energy and the environment, 443 Extinction of species, 271
Energy use, 443 Extremophiles, 247
Engine oil, recycling and reuse of, 398 Extruders
Envelope windows, problems with in recycling paper, 413 hydrogenations in, 209
“Envirocats”, 106 for increasing molecular weight by chain extension, 208
Environmental accounting, 499 polymerizations in, 209
Environmental backlash, 520–521 preparation of block and graft copolymers in, 208
Environmental chemistry reactions in, 207
books about, preface for removal of residual monomer from polymers, 208
definition of, preface
Environmental degradation, relation of overpopulation to, 461 Failure
Environmental economics, 497 of clothing, 390
Enzymes of coatings, 390
use in sc carbon dioxide, 246 of materials and equipment, 390
conjugation with polyethylene glycol, 246 of plastics, 391
directed evolution of, 247 Family planning, 485
use with gaseous substrates, 245 cost of, 492
for hydrolysis of nitriles, 255–256 Farm subsidies, deterrent to alternative agriculture, 348
use with ion exchange resins, 116 Fats and oils, hydrolysis and transesterification of, 251
made by solid state fermentations, 245 hydrogenation of, 370
use in organic solvents, 245–246 Fatty acids, omega-3
for oxidations, 81, 85, 249–251 Feathers, possible molding of, 376
for polymerizations, 263 Fermentation, products from, 242
for preparation of esters, 251 Ferrofluids, 110
for preparation of amides, 255 Fertility, declining, 481, 492
for reductions, 249–251 rates, 482
for repulping of paper, 413 Fertilization, chemistry of, 491
supported on silica, 108 Fertilizers, 344
use with surfactants, 246 run-off of, 324–325, 344
thermal stability of, 244, 246–248, 265 cost of, 498
Epibatidine, 45, 269 Fire supression without halons, 54
Epoxides, 18 Fish advisories, 12
preparation of, 58–59, 80, 83, 84, 86–87, 88, 90–91, 120, 122 Fish ladders, 448
asymmetric, 306–307, 309, 313 Fish, losses at power plants, 444
in sc carbon dioxide, 212 Fisheries, decline of, 497–498
electrochemical, 56 Flammable gases, accidents with, 8
with enzymes, 246 alternatives to, 9
with heteropolyacids, 160 Flame retardants, 402
from renewable raw materials, 368 Flame-sprayed coatings, 224
in water, 218 Flax and linen, 372
Epoxy resins, from sugars and vegetable oils, 378 Fluidized bed, recirculating reactor, 78
Esters and ethers, cleavage by sc water, 214 Fluorescent lamps, compact, 453
Estrogen mimics, 1, 49 Fluorinated solvents, 202
Estrogens, 484–485 Fluorocarbons, 54
Ethanol, dehydration of, 187 Fluorous biphasic systems, 175
for fuel, 456 Fly ash, 444
preparation by fermentation with continuous removal as uses for, 425
formed, 187, 190, 243 Food supplies, 482
from both 5 and 6 carbon sugars, 243 Foods, contaminants in, 3
Index 541

Formaldehyde, 32, 42, 76, 264 Halogens, made in situ from salts, 57
alternatives to, 366, 368, 371, 373 Halons, 54
reagents for crease-proofing made from, 74 Halogenated prophyrins, use in catalysts for oxidation, 91
replacement of, in preparation of ion exchange resins, 112 “Hairy root” culture, 274
Fouling organisms, 72 Hair sprays, 228
Fouling, animals resistant to Hazardous chemicals, replacement of, 27
Fuel cells, 458–459 use in manufacturing, 6
Fuel efficiency standards, 451 “Heat islands”, cities as, 451
Fuel prices, 446 Heat pumps, 451
Fuels, alternative, 456 Heat-sealing of plastics, 228
Fumigants, alternatives to, 338 Heat, solar, 459
Fumigation without methyl bromide, 54 storage of, 453
Fungi, control by bacteria and other fungi, 342 Heavy metal ions, 65
toxins from, 2 alternatives to the use of, 68
Fungicides, 321, 341–342 exposure limits, 68
Furfural, 378 recycling of, 68
recovery by ion exchange, 69
Gallium arsenide, synthesis and use, 75
recovery from waste water, 69
Gallophosphates, 147
Heck Reaction, 106, 115, 146
Gas-liquid-liquid systems, 175
in water, 15–217
Gas phase reactions, 203
Hemicellulose, 374
Gases, separation with membranes, 184, 189
xylitol from, 374
Gene transfer, 265–267
Hemp, 345
Genetic engineering, 265
Herbal supplements, 5
of crops, 346
Herbicides, 319
Germination, stimulants for, 340
crops tolerant to, 266
Geothermal energy, 462, 448
Gifts, unneeded and unwanted, 428 Heterogenization of homogeneous catalysts, 109, 122
Ginseng, 274 Heteropolyoxometallates
Global warming, 448 as acids, 157
attitude of companies toward, 450 antiviral activity of, 161
cost to mitigate, 450 in bleaching paper, 160
Glucose, oxidation to gluconic acid, 80 as catalysts, 157
Glycerol in clay, 156
enzymatic synthesis of, 257 in desulfurization of petroleum, 160
enzyme-catalyzed reactions of, 258 in oxidations, 80, 159–161
from microalgae, 257 in photochemical reactions, 160
oxidation to glyceric acid, 81 in preparation of esters, 157
polymers from, 376 pore size in, 156
Green accounting, 501 sandwich types, 160
Green chemistry, definition of, preface, 6 in solvent-free reactions, 207
field trips for course, preface on supports, 160–161
laboratory for course, preface 1,6-Hexamethylenediamine, 366
“Green Dot” system, 433 1-Hexene, preparation of, 362
Green garments, 73 Hidden costs, 518–519
Green labels, 431 of fertilizer, 506
Green taxes, 510 of food, 506
Greening, of companies, 522 of furniture, 505
of governments, 521 of landfills, 506
of individuals, 517 of waterfront lots, 506
of non-governmental organizations, 519 Highway run-off, 65
rhetoric versus reality, 523–529 Hindered amine light stabilizers, 395
Greenpeace, 58–59, 520 Hollow fiber membranes, 184
Greenwashing, 523 for removal of organic pollutants in water, 184
Grinding, use in reactions without solvent, 205 Hormones, mimics of, 49
Guanidinium sulfonates, 178 reproductive, 483, 485
Gypsy moth, 328–329 steroid, 484–486
542 Index

Host-guest complexes, 176 [Inclusion compounds]

Hot-melt adhesives, 227 from pyrazolones, 179
Household hazardous chemicals, 516 to reduce toxicity of guest, 177
Housekeeping in manufacturing plants, 13 Incompatible reagents, made compatible by use of supports, 123
Human error, role in accidents, 10–11 Indigo, 259
Hydration of olefins, with heteropolyoxometallates, 158 Indium(III) chloride, 142
Hydraulic fluids, from vegetable oil, 370 Indium, use in coatings for windows, 454
Hydrochlorofluorocarbons, 53 Individuals, environmental action by, 519
Hydrofluorocarbons, 53 environmental economics of, 505
Hydrofluoric acid, use in alkylations, 135, 147, 158 protests of abuses of companies by, 506
Hydroformylation, 121, 175–176, 211–212, 215, 220, 371 purchase of less-efficient items by, 505
asymmetric, 314 Industrial chemistry, books about, preface
in sc carbon dioxide, 213 definition of, preface
of propylene, 109 Inks, 227
in water, 217 for ballpoint pens, 227
Hydrogen cured by radiation, 226
from biomass, 371 Insect antifeedants, 269, 329–331
for fuel, 457 Insect growth regulators, 334
from glucose, 248, 458 Insect pheromones, 331
made by microorganisms, 457 Insecticides, natural, 3
photoelectrochemical generation of, 457 carbamates and organophosphates, 319
storage of, 458 Insects
storage as metal hydrides, 458 biological control of, 328
Hydrogen cyanide, 15–16 control by dyes with use of light, 338
in manufacture of glyphosate, 339 by fatty acid soaps, 339
use of, 9 by mechanical and cultural methods, 326
Hydrogen chloride, waste, reuse of, 58 by microwaves on grain, 326
Hydrogen peroxide, 50–51 by predators, parasites and pathogens, 327
manufacture of, 77 without use of methyl bromide, 54
Hydrogenation by viruses, 328
of aldehydes, 110 Insect viruses, genetic engineering of, 347
electrochemical, 465 Insulating windows with silica aerogels, 455
Hydrolysis or alcoholysis of polyamides, polycarbonates, Intercalation in clays, 154
polyesters, polyurethanes for Intercropping, 327
recycle, 417 for weed control, 339
Hydropower, 448, 462 Integrated pest management
Hydroquinone, 369 on apples and pears, 347
enzymatic preparation of, 259 on cotton, 347
Hydrotalcites, 83, 142–143 in Cuba, 348
Hydrotropes, 36, 218 on rice, 347
Hydroxycarboxylic acids, 255, 293–294 reasons for slow adoption of, 348
Hydroxylation, by enzymes, 255 International ecotreaties, 517, 522
of phenols, 249 Intrauterine devices, 486
Iodine as an oxidant, 90
Ibufprofen, 135 Iodoso compounds, use in oxidation, 89–90
ICI, spills at, 9 Ion exchange resins, 112–116, 136–138
Imidazolinones as agrochemicals, 320 use as catalysts, 113–114
Immobilization, of cells, 244 use in enzymatic reactions, 116
of enzymes, 244, 252 use in hydrogenation, 114
Imprinted polymers, preparation of, 297 as reagents, 113
in separations, 180 ways of wearing out, 113
Incineration of waste, 410–411 Ion exchange by zeolites, 152
Inclusion compounds, 176 Ionic liquids, 175, 203
from aryl sulfides, 179 Ions, separation of, 180
from carboxylic acids and their salts, 179 Iron-on patch for mending, 402
from diols, 178 Isobutane, alkylation with olefins, 135
from guanidinium salts, 178 preparation of, 159
Index 543

Isobutylene, conversion to methyl methacrylate, 159 Lawsuits, 2

polymerization without a chlorinated solvent, 56 Lead, 65–67, 69, 73–74, 76
preparation of, 149 Leaks, prevention of, 13–15
separation from mixed butenes, 175 at valves and seals, 13
Isobutyraldehyde, use of, 16–17 Leasing, saving money by instead of selling, 505
use in oxidations with oxygen, 80 Leather, finishing of, 75
Isocyanate-containing monomers, 36, 39 Lending organizations, international, 522
Isocyanates, addition to, 38 Less material used to make an object, 426
blocked, 38 but more profit, 505
use in powder coatings, 224 Levulinic acid, 341
preparation of, 28–38, 42 manufacture of, 366
by addition of urethanes to double bonds, 36 Lewis acids, polymeric, 137
from dialkyl carbonates, 29 Liability suits, 2
from isocyanic acid, 35 Libraries of compounds from combinatorial chemistry, 116
by nitrenes, 36 Life cycle analyses, 431, 499–501
from nitro compounds, 34 limitations of, 431, 500
without nitro compounds in the synthetic route, 42 Ligands, for metal ions, polymeric, 120
by rearrangements, 36 water-soluble, 216, 304
toxicity of the intermediates in, 41 use in biphasic reactions, 175
from ureas, 32, 42 Light, use as a “clean” reagent, 466
reduction of the toxicity of, 38 coatings cured by, 225
Isocyanatoethyl methacrylate, 36 Lighting, 74, 453
Isocyanic acid, 35 Light pipes, 453
N-Isopropylacrylamide, polymers of, 122 Light stabilizers, 394–395
Isosorbide, polymers from, 377 Lignin, for use in plastics, 374
ISO standards, 525 removal from wood with enzymes, 261
Isothiazolinones as biocides, 71–72 Lipases, 245, 248, 251–252, 261, 298
lipid-coated, 247
Jacobsen epoxidation of olefins, 307–308
Liquid membranes, 184
Jasmonic acid, 337
for separation of ions, 184
Jasminaldehyde, 151
Litigation against proposed regulations, 523
Jobs and regulations, 523
Long range transport of pollutants, 48, 58, 323, 502
myths about, 509
Longer wear, 389
Juvenile hormone, 334
Lubricants, 397–398
Kalundborg, Denmark, 432 vegetable oils as, 370, 399
Keggin ions, 157 Lubricity of metals, 76
Kenaf, 372 Luster pigments, 227
use in paper, 414 Lysergic acid, 3
Kerala, India, success in controlling population growth, 492
Macrocyclic ligands, use in separations, 181
Ketimines, use in coatings, 224
Magnesium oxide, 143
Ketones, preparation by oxidation of alcohols, 80, 87
Magnetic separations, 108
reduction of, 116
by enzymes, 250 Magnetic bearings, 397
Kinetic resolutions, 297, 301 Magnetic fields to prevent scale in water, 402
Knoevenagel Reaction, 142–143 Magnetic tape, coatings for, 228
Magnetite, use in separations by density, 174
Lamps, fluorescent, 74 as a support, 108
without mercury, 74 Malaria, 267
Landfills, 410, 419 Male contraceptives, 489
gas from, 457 Maleic anhydride, manufacture of, 365
tires in, 420 Manganese-containing catalysts for oxidations, 76, 83
Lauric acid, from genetically-modified rapeseed, 265 Marine algae, products from, 259
from petroselenic acid with ozone, 266 Marine refuges, 507
Lawns, 345 Mechanization through gadgets, 447
alternatives to, 346 Meerwein-Ponndorff-Verley Reduction, 142–143, 150
chemicals used on, 345 Melamine, 32
as sources of pollution, 345 manufacture of, 371
544 Index

Melt recrystallization, 203 Microreactors, 202

Melts, reactions in, 203 use in manufacture of methyl isocyanate, 29
Membrane bioreactors, 189, 249, 252 Microwave energy, use to accelerate chemical reactions,
Membrane reactors, 188, 301, 306–307 155–156, 467
to moderate exotherms, 189 use in reactions without solvent, 467
Membranes, chiral, 297, 301 Mitsunobu Reaction, 114
use in dehydrations, 187–188 Molecular sieves, 143–153
fouling of, 184 Molten metal baths, use to recover hydrogen and carbon
inorganic, 187–188 monoxide from organic waste, 425
preparation of, 184 Mono- and diglycerides, 252
use in separations, of carboxylic acids, 183 Monomers containing trialkoxysilane groups, 108
of chiral compounds, 186 Montreal protocol, 522
of copper sulfate, 183 Morning-after treatments, 487
of gases, 183 Mosquito control, 326
of olefins, 186 Multipurpose wet cleaning, 56
of phospholipids, 183 Municipal solid waste, 409
of fats and oils from waste water, 183 separation of, 411
of zeolites, 153 Mutagens, 4
Mending, 402 in diesel soot, 445
Menthol, manufacture of, 314 Mycorrhizae, 344
Mercury, 65–67, 70, 72, 74, 76 Mycotoxins, 2
in lamps, 454
from power plants, 443 “Nafion,” 136–137
removal from stack gases, 68 on supports, 137
replacement in a catalyst for hydration of acetylene, 114 nanocomposites, 398
separation by a zeolite, 152 nanofiltration, 183
in water, 12 “Natural,” 2
Merrifield resin, 116–117 Natural capital, 499
use in solid-phase synthesis of polypeptides, 116 Natural polymers, 372
Mesoporous solids, 145, 151–152 Natural resource depletion, 505
Metabolic engineering, 258 Nature’s services, 497
Metal oxides, sulfated, 138 Neem tree, 329
supported, 139 Nematode control, 326–327
Neodymium(III) chloride, use in alkylation of aromatic
Metal clusters, colloidal, 110
hydrocarbons, 154
as models for heterogeneous catalysts, 110
Newspapers, 430
Metal deactivators, 394
Nickel, 65–67, 69
Metal finishing, 75
Nitriles, hydrolysis of, 103
Metal ions, toxic heavy, 65
Nitration of aromatic hydrocarbons, 148, 155
Metals, from petroleum residues, 423
Nitrogen fixation, 447
recovery with enzymes, 261–262
by bacteria, 344
Methacrylic acid, synthesis from citric acid, 215
Nitrogen oxides, from burning fuels, 443
Methane, use as a fuel, 456
use to oxidize benzene to phenol, 82
Methanol, use in alkylating hydroquinone, 213
NGOs, 519
Methylamines, manufacture using zeolites, 150
Nongovernmental organizations, 519
Methyl anthranilate, use as bird repellent, 331
antienvironmental ones, 520
Methyl bromide, 324, 338
size of membership, 520
alternatives for, 54 Nuclear energy, 7–8, 448
Methyl ether, use as a fuel, 456 contamination from use of, 7
Methyl isocyanate, accident at Bhopal, India problems in plants using, 8
manufacture of, 28–29 safety in plants using, 7
Methyl methacrylate, manufacture of, 9 waste from, 2
Methyl parathion, 323 Nylon, use of byproducts from manufacture, 14
Microemulsions, reactions in, 218
Microfiltration, 183 Obesity, premature deaths from, 4
Microporous solids, 143, 146 Ocean thermal systems to generate electricity, 459–460
Mifepristone, 487 Office of Technology Assessment, 521
Index 545

Office waste paper, 430 [Paper]

Oil, extraction from plants with enzymes, 262 preparation,
improper disposal of used engine, 425 from bagasse, 414
spills, 10, 12, 526–529 from kenaf, 414
Olefins, catalysts for polymerization of, 18 from straw, 414
copolymerization with carbon monoxide, 362 from non-wood sources, 414
dihydroxylation of, 120 sizing with resin acids, 371
preparation by dehydration of alcohols with clay catalysts, waste, non-paper uses for, 414
156 Paper or plastic, choice of, 500
preparation from renewable raw materials, 362 Parasitoids, 334
On-line monitoring of reactions to reduce waste, 15, 174 Particulate matter, fine, from power plants, 444
Optical isomers, 291 Passive solar heating and cooling, 451
effects of unwanted isomer, 291 PCBs, 1, 12, 48
separation by use of inclusion compounds, 177 Peltier effect, 453
Oral contraceptives, 485–486 Penicillin, enzymatic reactions of, 256–257
Organic farming, 348 Penicillin acylases, 256–257
Osmium compounds on supports, 309 Pentachlorophenol, 70
Overconsumption, 498–499 Peptides, 245
of materials by society, 403 Perfluorocarbons, 54
Overpopulation, 461 Periodates, use in oxidation, 92
Oviposition attractants, 334 Permanent-press fabrics, 74
Oxidation, 76 Peroxidases, 264
of alcohols to aldehydes, 120, 122 Peroxide decomposers, 393
chiral, 306–309 Peroxides, test for, 83
Pervaporation, for separation of water and ethanol, 187
in carbon dioxide, 211, 213
for removal of organic compounds from waste water, 188
with dinitrogen oxide, 92
Persistent organic pollutants, 1, 48
electrochemical, 90, 465
Pesticides, 319
using enzymes, 81, 85
in air and water, 323
with light, 466
effects on non-target organisms, 322
with halogen and halogen-containing compounds, 90
metabolites of, 324
with heavy metal ions, 76
poisonings from, 322–323
without heavy metal ions, 77
selectivities of, 322
with hydrogen peroxide and reagents derived from it, 77, 88
Petroselenic acid, 266
by hydroperoxides, 86 Phase transfer catalysts, chiral, 312
initiation of, 391 polymeric, 119
of ligands in metal-containing oxidizing agents, 77 solid, 156
with manganese-containing compounds, 76 Phenol, enzymatic reactions of, 249
using oxygen, 77–78 manufacture from benzene, 82–83, 122
using ozone, 77 oxidation of, 87
using supported reagents, 77 resins from, 264
in zeolites, 83 Pheromones, 331
Oxygen, barrier coatings for, 226 traps for insects, 332
separation from nitrogen with membranes, 188 Phosgene, 27
Ozone, hydrogen and peracids, use as biocides, 71 Phosphate, in detergents, replacements for, 221
depletion of stratospheric, 52 as fertilizer, 344
at ground level 445 separation from water, 181
Ozone hole, 52 Photochemical reactions, 466
Photodegradants for polymers, 420
Packaging, minimizing, 428 Photography, without silver, 74
Paint, latex, 221 Photoinitiators for coatings, 225
Paint, stripping without methylene chloride, 56 Photovoltaic cells:
Paper of amorphous silicon, 460
bleaching (See also Bleaching paper) of cadmium telluride, 461
deinking of used, 411 of copper indium diselenide, 461
flotation in, 412 of gallium arsenide, 461
mill sludge, uses for, 414 heavy metals in, 75
minimization of use, 430 manufacture of, 460
546 Index

[Photovoltaic cells:] [Polymerization]

maximizing absorption of light, 460 of lactones and carbonates, 263
minimizing reflection from, 460 in plasmas, 226
of polycrystalline silicon, 460 in solid state, use of microwaves with, 467
of single crystals of silicon, 460 Polyolefins, 18
stacked, 461 to replace poly(vinyl chloride), 19
tandem, 461 Polysiloxanes, 265
Phthalate plasticizers, 49 Polymers, preparation in cyclodextrins, 125
Phthalic anhydride, manufacture of, 365 with inverse temperature solubility, 122
Phytoalexins, in control of insects, 336 preparation by Diels-Alder Reaction, 380–381
elicitors for, 337 from sorbic acid, 380
Pickle liquor, reuse of, 15 Polymer-supported catalysts, 104, 111
Pigments, 73 Lewis acids, 137
from fungi, 262 Polyureas, coatings of, 226
Pinacol rearrangement, 136 Polyurethanes, 379
-Pinene, oxidation of, 80–81 manufacture of, 28
Plant and animal pathogens, control of, 341 waterborne, 38
Plant biotechnology, 265 Poly(vinyl chloride), replacement of, 49–50, 58
Plant cell and tissue culture, 274 replacement by poly(lactic acids), 379
Plant growth inhibitors, 340 replacement by polyolefins, 19, 362, 391
Plasma, arc to recover hydrogen and carbon monoxide from stabilizers for, 66, 72
organic waste, 425 Population and the environment, 483
deposition of coatings, 226 Population growth rates, 483
polymerization in, 226 Potassium ferrate, use in oxidation, 76
Plastics, reduction of wear by, 397 fluoride on alumina, use as a base, 103, 142
Plasticizers, loss of, 49, 390 peroxymonosulfate, use in oxidation, 89
Poverty and malnutrition, 482
Plastisols, 226
Precautionary principle, 507
Poisonings, from pesticides, 4
Pregnancies, unintended, 485
Pollinators, natural, 323
Preventing loss of expensive or toxic materials, use of supports
Pollution Prevention Act of 1990, preface
for, 120
Pollution prevention, incentives for, 503
Printing, 227
individuals and, 503–504
“Proactive” companies, 526
money saved, 503
Process intensification, 29, 202
reasons for slowness of adoption, 503
Progestins, 485
Polyamides, biodegradable packaging from adipic acid, amino
Progesterone, 484, 486
acids and 1,6-hexamethylenediamine, 379
synthesis of, 91
from fatty acids, 379 Propanediols, manufacture of, 258, 364
Poly(amino acids), 379 Propionic acid, preparation by fermentation, 254
Poly(aspartic acid), 379 Propylene, hydroformylation of, 16, 109
Polycarbonates, 39 manufacture of, 362–363
Polychlorinated biphenyls, 1, 12, 48 from methanol, 149
Polyesters, preparation with enzymes, 263 Propylene oxide, manufacture of, 18, 56, 58, 78, 86, 147, 363
Poly(ethylene glycol), use as a reaction medium, 220 Protecting groups, polymeric, 123
Poly(ethylene terephthalate), use of byproducts from Proteins, in adhesives, 376
manufacture of, 15 cross-linking of, 376
Poly(ethyleneimine), use as a support, 120 films of, 375
Poly(gamma-glutamic acid), 379 improving water resistance of, 376
Poly(hydroxyalkanoates), 263, 379 molded, 374
Polyimides, use in membranes, 186 plasticizers for, 374
Poly(lactic acid), 379 Pulping of wood, 374
Polyleucine, 306–307 Pyrolysis of plastics, 419
Polymeric reagents, 113, 118
Polymeric sulfonic acids, 136–137 Quinacrine, 490
Polymerization, enzymatic, 263 Quaternary ammonium and phosphonium salts, use as biocides,
in extruders, 209 71
in flight for coatings, 226 Quinone-amine polymers, 227
Index 547

Racemization of optical isomers, 296 [Recycling]

Radioactive contamination, 7 contaminants in, 412
Random mutagenesis, 248 wax, 412
Rare earth triflates, 139 windows in envelopes, 413
microencapsulation of, 139 “stickies”, 412
use as polymerization catalysts, 141 deinking, 411
Rating systems for consumer items, 403 enzymatic repulping, 413
Raw materials, unsustainable use of, 504 extent of, 413
Rayon, 18 repulping of, 411
Reaction injection molding, 209–210 toner removal, 412
Reactions of phenolic resins, 418
in carbon dioxide, 210 of plastics, 415
by chemical reactions, 417
in extruders, 207–208
problems of, 415
hydrogenations, 209
pyrolysis to monomer, 208, 419
to prepare block copolymers, 208
of poly(ethylene terephthalate), 416
in the gas phase, 203
of polystyrene, 416, 419
in melts, 203
of polyurethanes, 418
without solvent, 203–207 of poly(vinyl chloride), 416
isolation of products, 204 problems of, 410
with microwaves, 204 rates of, 409–410
in water, 214–220 of rubber, 420
in microemulsions, 218 of salts formed in separations, 176
organometallic, 216 of surgical instruments, 427
in suspension, 220 of textiles, 424
Reactive distillation, 147, 175 of toner cartridges, 425
Recovery, of acids and bases from waste salts by electrodialysis, of wood and construction wastes, 424
183 Reduction of alkynes, 121
of carboxylic acids, 183, 189 of consumption, 432
of solvents, 202 Refrigerants, other than CFCs, 55
Recrystallization from melts, 203 Refrigeration, without refrigerants, 55
Recycled content, laws governing, 432 with solar energy, 452
Recycling Regulations, costs of, 501, 523
of antifreeze, 425 to curb abuses, 508
of batterries, 68 flexibility in, 8, 524
of bleaching earth, 426 litigation to prevent implementation, 510
of byproducts of the manufacturing of aluminum and steel, Renewable energy, 456
422 resources, 361
of carpet, 425 Reproductive health services, 492
of clothing, 425 hormones, 483
Resistance to pesticides, 322
economics of, 432
Resolution of racemic mixtures, 295
of fluorescent lamps, 423
use of chiral columns in, 297
of food processing wastes, 424
use of chiral membranes, 297
in Germany, 433
diastereoisomeric, 297
of glass, 423
dynamic, 299
to fiber glass, 423 use of enzymes in, 297–300, 306
into glassphalt, 423 by inclusion compounds, 295
of high density polyethylene milk jugs, 416 by kinetic resolution, 297
of ink, 425 with more than 50% yields, 299
jobs in, 433 with simultaneous racemization of the unwanted isomer, 299
labels on plastics, 416 Responsible care, 524
of metals, 422 Resin acids, 371
of nylon, 418 Resveratrol, 4
of oil, 425 Reusable items, 427
of paint, 425 Reuse of clothing, 425
of paper, 413 Reverse osmosis, 183
548 Index

Rhenium catalysts, use in oxidations, 84–85 [Separations]

Right-to-know laws, use to reduce pollution, 508–509 of oxygen and nitrogen with membranes, 185, 189
Rotation of crops, 326 of phosphate in water, 181
RU 486, 487 of phospholipids, 183
Rubber by physical means, 173
use in asphalt, 421 by reacting out a compound from a mixture, 175
devulcanization of, 421 by size and shape, 176–180
powder from used tires, treatment for use in new polymers, of sugars, 181
421 with zeolite films, 187
use in toughening plastics, 390 “Sevin”, 29
Seaweed, products from, 259
Sabadilla, 3 Sharing tools and equipment, 428
Saccharin, 3 Sharpless dihydroxylation of olefins, 308
Safety in chemical manufacturing, 6 Silanetriols, use in formation of metal clusters, 110
at nuclear plants, 7 Silasesquioxanes, 110–111
Safrole in root beer, 3 Silica, aerogels in windows, 455
Salt consumption in relation to health, 4 coatings of, 226
Scale in water, prevention by magnetic fields, 402 use as a support, reactions on, 103–104
Scandium dodecyl sulfate, 142 Silicoaluminophosphates (SAPOs), 149–150
Scientists, attitudes toward, 2 Silicon-containing membranes, 186–187
Scratch-resistance, of coatings, 226 Siloxane polymerase, 265
of plastics, 110, 226 Single cell protein, 263
Screen printing, 227 Simulated moving bed chromatography, 197
Sealants, 228 Single use throw-away items, 427, 447
Selectivity in reactions by size and shape, 136, 148–150, 155 selection by individuals, 505
Selenium, 65, 81 Site isolation in solid catalysts, 105, 120
Self-cleaning coatings of titanium dioxide, 56, 222 Slash and burn agriculture, 481
Self-lubricating plastic gears, 397 “Smart” catalysts, 122
Separations, 173–190 windows, 454
of anions with membranes, 184 Smoking deaths, 4
between two aqueous phases, 176 Soap, 220–221
in biphasic reactions, 173 Soda bottles of poly(ethylene terephthalate), refillable, 226
of butanes with zeolites, 153 Sodium, use on a support, 103
with calixarenes, 178 Sodium chloride, consumption in relation to health, 4
of carbon dioxide from nitrogen, 185 Sodium hypochlorite, use in oxidations, 91
of carboxylic acids, 176, 183 Sodium perborate, 77, 85
of citric acid, 181 use in asymmetric oxidations, 307
by continuous extraction as the product is formed, 175 Sodium percarbonate, 77, 85
of copper sulfate, 183 Sodium tripolyphosphate, 147, 221
with crown ethers, 178 replacements for, 80
by density, 174 Soft drinks, composition of, 429
factors in, 184 consumption of, 429
by flotation, 174 Solar cells (See photovoltaic cells)
with guanidinium sulfonates, 178 chimneys, to generate electricity, 459
with imprinted polymers, 180 cooker, 452
with inclusion compounds, 176 heating and cooling, 451–452
using inverse temperature solubility of a polymer, 122 home in Germany not connected with the electric grid, 462
of ions, 180 ponds, use to generate electricity, 459
use of light in, 173–174 thermal systems, 452, 459
magnetic, 173–174 absorbers for, 459
with membranes, 183 parabolic dishes for, 459
of metal ions by use of chelating agents, 69 towers, use for generation of electricity, 459
of mixed municipal waste, 174 Sol-gel method, 244
of mixed plastics with solvents, 417 catalysts made by, 109
of optical isomers, 177 Solid acids and bases, 135–161
of organic vapors from air with membranes, 185–186 Solid bases, 142–143
Index 549

Solid catalysts and reagents Supported catalysts, loss of catalyst during the reaction, 120
advantages and disadvantages, 101 preparation using alkoxysilanes, 106
preparation of, 102 structure of, 138
Solid-phase synthesis of polypeptides, 116 Supported Lewis acids, 137
Solid-state synthesis, 207 liquid films on solids, 104
Soil loss, 325–326 metal chlorides, 105–106
Solvents, advantages and disadvantages, 201 metal oxides, 139
chlorinated, 55 noble metal catalysts, 109
emissions, sources of, 201 oxidizing agents, 77, 80, 83, 86–89
less toxic, 202 for polymerization of olefins, 109
prevention of loss of, 13 Supports, inorganic, for catalysts and reagents, 103
recovery of, 13 to prevent loss of expensive or toxic materials, 120
from emissions, 202 reaction of catalyst with, 106
working without, 201, 203–204 for solid catalysts and reagents, 101, 103
Sorbitol, manufacture of, 364 Surfactants, 220
Source reduction, 426 destructible, 220
Spermicides, 487 use with enzymes, 246
Spider silk, 376 problems with, 221
Stability of polymers, 391 from renewable raw materials, 222
Stabilizers Sustainable agriculture, 324, 348
cyclodextrins as, 124 economy, materials for, 361
for insect viruses, 329 future, 19
for polymers, 391 definition of, preface
Starch, films of, 374 Synthesis gas, from biomass, 371
molded, 208, 373 conversion to aromatic compounds, 371
Steel minimills, 422 gasoline, 371
Stone buildings, decay of, 400 methanol, 371
Storage of energy, 453, 463 (See also energy storage.) olefins, 371
Stoves, wood, contamination from, 446 Synthetic oils, esters as, 399
Stereochemistry, 291 silicones as, 399
Sterilization, 490
non-surgical, 490–491 Tanning leather without chromium, 75
Subsidies, effects on natural resource depletion, 509 Tannins, use in resins, 369
on virgin materials, 432 Tapes, coatings, 228
Succinic acid, manufacture of, 254, 365 Tartaric acid, 294, 297
Sucrose, vinyl monomers from, 263 Taxes, to curb abuses, 507, 510
Sugars, 293–294 energy, 510
monomers from, 377 shift to waste and pollution, 510
separation of, with arylboronic acids, 181 “Taxol,” preparation by cell culture, 275
Sulfated zirconia, 138 Terephthalic acid, preparation from renewable raw materials,
Sulfonic acids, polymeric, 136–138 368
Sulfonylureas, 320 Terpenes, 293, 295, 302
Sulfur, biological removal from petroleum, 262 as attractants and deterrents for insects, 333, 337
use in lamp, 453 use in control of plant pathogens, 342
Sulfur dioxide, from burning fuels, 443–444 use in control of termites, 342
removal of, 502 Tetraethyllead, 2
by zeolites, 152 Tetrahydrofuran, preparation of, 363, 366
from smelters, 67 Tetrodotoxin, 3
Sulfur hexafluoride, 53, 449 Textiles, biofinishing of, 261
Sulfuric acid, 135, 147, 151 finished without toxic reagents, 73
release of, 528–529 Thalidomide, 1
Superabsorbents, from sugars, 263, 377 Thermophilic organisms, 247
Superacids, 136, 138 Threatened and endangered species, 271
Superfund sites, 521 Throw-away items compared to reusable ones, 426
effects on health, 5 Tidal energy, 462
Supplements, dietary, 5 Tin, 65–66, 71
550 Index

Tires, burned for energy, 421 Vaccines, research on, 492

fires of, 421 Vegetable oils, use as lubricants, 370, 399
longer-wearing, 420 Vinyl esters, use in enzymatic esterifications, 252–253
use of powdered, 421 Vitamin E, 396
use of used, 420 Vitamin K, preparation without chromium, 84–85
Tissue culture, 274
Titanium-containing catalysts, use in oxidations, 88 Wacker Reaction, 120, 125, 159
Titanium dioxide, use in disinfection of water, 52 Waste, combustion of, 49
use as a pigment, 65 exchanges for, 15
use in self-cleaning coatings, 56 heat, from power plants, 445
Titanium silicalite, 87, 146, 157 recovery by metal hydrides, 458
Tortillas, pollution from cooking, 448 from industries, 503
Toxic chemicals, made on demand, rather than stored, 527 minimization of, 13–19, 409, 426
inventories of, 508–509 reasons for not being done, 503
Toxic oil syndrome, 5 reuse of, 15
Toxic Release Inventory, 11–12 salts containing chlorine, 56
Toxicity, of chlorine-containing compounds, 48 shipped abroad, 507
of heavy metal ions, 65 Water, acceleration of reactions in, 215
trade-offs, 41 bottled, 429
testing, variables in, 6 quality of, 430
Toxins, natural, 2 for cleavage of asters and ethers, 214
Trade associations, slow rate of “greening”, 523 disinfection of, by polymeric reagents, 118
Transgenic animals, 266 for destruction of organic compounds under supercritical
plants, 65–267, 346 conditions, 214
resistance to herbicides, 266, 347 ligands soluble in, 216
to insects, 266, 346 pollution of, 12
for producing antibodies, 266 as a reaction medium, 214–220
questions about use, 346–347 Wave energy, 463
Transportation, energy for, 445 Websites for environmental data preface
Trap crops, 327 Weak spots, in clothing and equipment, 389, 402
Traps for insects, electrical, 326 Wear, 397
Trehalose, 248 reduction by use of hard materials, 397–398
to stabilize enzymes, 248 Wearing out, reasons, 389
Weeds control
Trialkoxysilanes, 244
by allelopathy, 340
monomers containing, 108
by crop rotation, 339
Tricarboxylic acids, separation of, 181
by intercropping, 339
Triflates, metal, 139
invasive, 266
Triphase catalysis, 119
by light with delta-aminolevulinic acid, 341
Triphosgene, 27
by mechanical and cultural methods, 339
Tris(pentafluorophenyl)boron, 142
by mulching, 340
Tryptophan, deaths from impure, 5
by predators and pathogens, 340
Tunstated zirconia, 138
“Wheat Board”, 379
Tungsten oxide, use in windows, 455
Windows, electrochromic, 454–455
insulated with silica aerogels, 455
Ultrafiltration, 183
low-emissivity coatings for, 454
Ultrasonic energy, in extruder for the devulcanization of rubber,
photochromic, 454
421
Windpower, 462
for preparation of block copolymers, 467 Wood preservation, 70
use in reactions, 466 with copper chromium arsenate, 343
use in welding, 228 with terpenes, 343
Ultraviolet screening agents, 394 Wool, shrink-proofing without the use of chlorine, 51
United Nations, international conferences of, 522 World Bank, 522
Urban sprawl, alternatives to, 446 World Trade Organization, 522
Ureas, inclusion compounds from, 177
Urea peroxide, 77, 85–86 Xenon lamps, 454
Ureas, use in preparation of isocyaneates, 32 Xylanases, use in making paper, 51, 261
Index 551

Xylitol, 243 [Zeolites]

p-Xylene, 148, 158 pore sizes of, 144–145
preparation of, 145
microwave use in, 467
Zeolites, 143–153 modification after, 146
use as acids, 147 removal of templates from, 145
use as bases, 147 templates for, 145–146
use as catalysts for acylation and alkylation, 147–149 reactions in, 148–152
for polymerization, 152 use in separations, 147
use in detergents, 147 of butanes, 153
films of used in separations, 187 of dioxins, mercury and sulfur dioxide, 152
use in ion exchange, 152 stability of, 146
membranes, 153 stabilization of metal complexes by, 146
metal clusters and complexes in, 146 uses for, 147
names of, 145 Zero risk, 3
use in oxidations, 82–83, 88, 92 Zinc, 65–66, 68–69, 75–76
photochemical reactions in, 151 Zinc phosphate coatings to prevent corosion, 401
plugging of pores in, 142 Zirconia, sulfated, 138
polymerization in, 152 Zirconia, tungstated, 138